19. Norddeutsches Doktorandenkolloquium der Anorganischen Chemie. 15./16. September 2016 Hamburg. NordDeutsches

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1 19. Norddeutsches Doktorandenkolloquium der Anorganischen Chemie 15./16. September 2016 Hamburg vecteezy.com NordDeutsches DoktorandenKolloquium Organisation durch das Institut für Anorganische und Angewandte Chemie

2 Grußwort zum 19. Norddeutschen Doktoranden Kolloquium Liebe Kolleginnen und Kollegen, liebe Doktorandinnen und Doktoranden, im Namen des Instituts für Anorganische und Angewandte Chemie der Universität Hamburg möchten wir Sie herzlich willkommen heißen und freuen uns, Sie zum 19. Norddeutschen Doktorandenkolloquium (NDDK) begrüßen zu dürfen. Das erste NDDK wurde vor 19 Jahren in Hamburg mit Unterstützung durch den Verbund Norddeutscher Universitäten etabliert und ist inzwischen von allen teilnehmenden Arbeitsgruppen organisiert worden. Jetzt ist das NDDK wieder nach Hamburg zurückgekehrt. Es hat das erklärte Ziel, ein Forum für den wissenschaftlichen Austausch unter den Doktorandinnen und Doktoranden aus unterschiedlichsten Forschungsgebieten der Anorganischen Chemie zu schaffen. Darüber hinaus bietet es auch den Arbeitsgruppenleitern beste Gelegenheit, im direkten Gespräch über neuste Entwicklungen in der Anorganischen Chemie zu diskutieren und über neue Kooperationen und Projekte nachzudenken. Die konstante Zahl an angemeldeten Wissenschaftlern (ca. 90) spricht für die Attraktivität dieser Veranstaltung. Wir können uns auf insgesamt 25 angemeldete Vorträge und 37 Poster freuen, die wieder eine spannende Veranstaltung erwarten lassen. Das NDDK war ursprünglich so konzipiert, dass möglichst keine Kosten für die Organisatoren und die Doktorandinnen und Doktoranden entstehen. Dafür sind Sponsoren angesprochen worden. Mit ihrer finanziellen Hilfe ist es gelungen, unser Konzept wiederum zu verwirklichen. Dafür danken wir den Sponsoren ganz herzlich. Wir danken auch den vielen fleißigen Helfern, die das Gelingen dieser Veranstaltung erst ermöglichen. Wir freuen uns auf zwei spannende Tage mit vielen Diskussionen, nicht nur über schöne Chemie. Mit herzlichen Grüßen, Peter Burger und Jürgen Heck

3 Willkommen am Fachbereich Chemie! Moin, unser Fachbereich zählt zu den größten chemischen Fachbereichen der Bundesrepublik - so steht es zumindest auf unserer Homepage. Außerdem liegt er mitten in der wunderschönen Stadt Hamburch. Damit man sich ein bisschen besser zurechtfindet, sind hier einige nützliche Informationen: Die Vorträge des NDDK finden dieses Jahr in unserem Hörsaal B statt, den man bequem per Bus vom Bahnhof Dammtor, Hbf/Mönckebergstraße oder ZOB mit der Buslinie 4 oder 5 (Richtung Burgwedel, Nedderfeld oder Wildacker) erreichen kann. Der Weg zum Hörsaalfoyer ist von der Bushaltestelle Grindelhof auf der Grindelallee über den Martin-Luther-King-Platz zu erreichen, wenn man das Zoologische Museum linkerhand hinter sich lässt. Für alle Autofahrer aufgepasst, denn um unseren Fachbereich herum wird gerade mächtig gebaut, weswegen man hier häufig auf Durchfahrt verboten Schilder trifft, da braucht man etwas Geduld und Ruhe, um den richtigen Weg bzw. Parkplatz zu finden. Die Bundesstraße kann nur von Richtung Schlump befahren werden, wenn man zum Eingang Sedanstraße will.

4 Genächtigt wird im Hotel Alsterhof (Esplanade 12, siehe Kartenausschnitt). Wir empfehlen direkt vom Bahnhof Dammtor zu Fuß am Donnerstag zum Hotel zu gehen und dort schon mal das Gepäck unterzubringen. Zu den Vorträgen am Fachbereich kann man dann gemütlich mit dem Bus Linie 4 oder 5 von der Bushaltestelle Stephansplatz bis zur Haltestelle Grindelhof fahren oder für die Sportlicheren den Weg auch zu Fuß bewältigen. Wer nach der Poster-Session ins Fahrwasser geraten sollte, kann sich dann noch ins Zentrum hamburgischen, hanseatischen Geschnackes werfen auf zum Elb- oder Alsterufer! Die S/UBahnstationen Jungfernstieg, St. Pauli und Reeperbahn sind dann auch nur einen Katzensprung entfernt. Middenmang as blots dorbie! Viel Spaß auf dem 19. NDDK in Hamburg!

5 Inhaltsverzeichnis 1. Sponsoren und Förderer 5 2. Ausrichter des Norddeutschen Doktorandenkolloquiums 6 3. Tagungsprogramm 7 4. Vortragsprogramm 8 5. Abstracts der Vorträge Session 1: Koordinationschemie 12 Session 2: Theorie- und Festkörperchemie 18 Session 3: Hauptgruppenchemie 25 Session 4: Metallorganische Chemie Posterprogramm Abstracts der Poster Liste der Teilnehmerinnen und Teilnehmer 81

6 Wir danken folgenden Firmen und Institutionen sehr herzlich: Freundes- und Förderverein Chemie der Universität Hamburg e.v.

7 Ausrichter des Norddeutschen Doktorandenkolloquiums 2016 Universität Hamburg 2015 Georg-August Universität Göttingen 2014 LIKAT Rostock 2013 Universität Bremen 2012 Christian-Albrechts-Universität zu Kiel 2011 Leibnitz Universität Hannover 2010 Ernst-Moritz-Universität Greifswald 2009 Carl von Ossietzky Universität Oldenburg 2008 Technische Universität Braunschweig 2007 Jacobs Universität Bremen 2006 Universität Rostock 2005 Universität Rostock 2004 Universität Hamburg 2003 Universität Hamburg 2002 Universität Hamburg 2001 Universität Hamburg 2000 Universität Hamburg 1999 Universität Hamburg 1998 Universität Hamburg

8 Tagungsprogramm Donnerstag, Bis 13:00 Uhr Anfahrt und Registrierung Hörsaalfoyer 13:00 Uhr Begrüßung Hörsaal B 13:10 Uhr Vorträge (Session 1) Hörsaal B 15:10 Uhr Kaffeepause Hörsaalfoyer 15:30 Uhr Vorträge (Session 2) Hörsaal B 17:50 Uhr Ende 18:00 Uhr Sitzung der AK-Leiter Seminarraum AC S1 Ab 18:30 Uhr Grillen Martin-Luther-King-Platz Ab 20:30 Uhr Postersession Glasgang 8:30 Uhr Vorträge (Session 3) Hörsaal B 10:30 Uhr Kaffeepause Hörsaalfoyer 11:00 Uhr Vorträge (Session 4) Hörsaal B 13:00 Uhr Vergabe der Präsentationspreise Verabschiedung und Abreise 13:30 Uhr Ende der Veranstaltung Freitag, Je Vortrag 20 Minuten

9 Vortragsprogramm Donnerstag, Session 1: Koordinationschemie Sitzungsleitung: Steve Waitschat, Universität Kiel 13:10 Uhr A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity Florian Schendzielorz, AK Schneider, Institut für Anorganische Chemie, Georg-August-Universität Göttingen 13:30 Uhr Group 10 Metal POCOP Fluoride Complexes for Halogen and Hydrogen Bonding Markus Joksch, AK Beweries, Leibniz Institute for Catalysis at the University of Rostock (LIKAT) 13:50 Uhr Clustersäuren und Clusterröhren Jonas König, AK Köckerling, Institut für Chemie, Universität Rostock 14:10 Uhr Applications of N-Heterocyclic Carbene-Phosphinidenes in the Stabilization of Reactive Main-Group and Transition Metal Organometallic Fragments Adinarayana Doddi, AK Tamm, Technical University Braunschweig 14:30 Uhr Speciation Studies and Bond Dissociation Free Energy of Cobalt Complexes with NH-Pyrazolyl Units Mona Wilken, AK Siewert, Institute for Inorganic Chemistry, GeorgAugust-University Göttingen 14:50 Uhr Synthesis and Characterization of Co9-Containing Heteropolyanion Muhammad Qasim, AK Kortz, Department of Life Sciences and Chemistry, Jacobs University Bremen

10 Session 2: Theorie- und Festkörperchemie Sitzungsleitung: Mona Wilken, Universität Göttingen 15:30 Uhr Continuous flow synthesis of Zr-MOFs with UiO-66 framework structure leading to high space time and real time yields Steve Waitschat, AK Stock, Institut für Anorganische Chemie, ChristianAlbrechts Universität zu Kiel 15:50 Uhr Influence of exact Exchange on the Diradical Character B. Alexander Voigt, AK Herrmann, Institute for Inorganic and Applied Chemistry, University of Hamburg 16:10 Uhr Low-temperature NH3-SCR of NO over excellent performing catalysts V2O5/Ce1-xTixO2 studied by operando spectroscopies T. H. Vuong, AK Brückner Leibniz Institute for Catalysis at the University of Rostock 16:30 Uhr Synthesis and characterization of visible light photocatalytic active Bi2WO6 coated TiO2 inverse opals Michael Teck, AK Gesing, Institut für Anorganische Chemie und Kristallographie, Universität Bremen 16:50 Uhr Cooperative assembly synthesis of mesoporous SrTiO3 with enhanced photocatalytic activity Bugra Kayaalp, AK Mascotto, Institut für Anorganische und Angewandte Chemie, Universität Hamburg 17:10 Uhr Deliquescence behavior of NaCl confined in nanopores Tanya Talreja, AK Steiger, Institut für Anorganische und Angewandte Chemie, Universität Hamburg 17:30 Uhr Spin switchable Ni(II) salpn-complexes for functional MRI contrast agents Brandenburg Hannah, AK Tuczek;Institut für Amnorganische Chemie, Christian-Albrechts-Universtitä Kiel

11 Freitag, Session 3: Hauptgruppenchemie Sitzungsleitung: Moritz Horstmann, Universität Rostock 8:30 Uhr Activation of 7-Silanorbornadienes by N-Heterocyclic Carbenes A Selective Way to NHC-Stabilized Silylenes Dennis Lutters, AK Müller, Institute of Chemistry, Carl von Ossietzky University of Oldenburg 8:50 Uhr Kupplungsfähige Fluoroionophore Für die Detektion von Kalium- und Natrium-Ionen im Lysosom Tobias Sprenger, AK Holdt, Anorganische Chemie, Universität Potsdam 9.10 Uhr Synthesis of circular P-N-P containing ligands Martha Höhne, AK Rosenthal, Leibniz Institute for Catalysis at the University of Rostock (LIKAT) 9:30 Uhr Intramolecular Lewis-Pairs Felix Kutter, AK Beckmann, Institut für anorganische Chemie und Kristallographie, Universität Bremen 9:50 Uhr Investigating the bonding situation in main-group element oxygen bonds Malte Fugel, AK Grabowsky, Institut für Anorganische Chemie und Kristallographie, Universität Bremen Uhr Isolation of labile pseudohalogen species NSO René Labbow, AK Schulz, Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock

12 Session 4: Metallorganische Chemie Sitzungsleitung: Dennis Lutters, Universität Oldenburg 11:00 Uhr 11:20 Uhr 11:40 Uhr 12:00 Uhr 12:20 Uhr 12:40 Uhr C H-Aktivierung sekundärer Amine Ausbildung von Titanacyclen und deren Folgechemie Manfred Manßen, AK Beckhaus, Institut für Chemie, Carl von Ossietzky Universität Oldenburg NH activation of ammonia by Rhodium complexes containing diphosphines Moritz Horstmann, AK Heller, Leibniz Institut für Katalyse, Universität Rostock Synthesis and Coordination Chemistry of new α-oxygen Substituted Alkyne Complexes Christopher Timmermann, AK Seidel, University of Rostock Synthesis of pyrazine-pyrane-dithiolene complexes mimicing specific features of the molybdenum cofactor (MoCo) C. Schindler, AK Schulzke, Institut für Biochemie, Ernst-Moritz-Arndt Universität Greifswald P-MOFs with Potentially Coordinating Secondary Sites Timo Stein, AK Fröba, Institute of Inorganic and Applied Chemistry, University of Hamburg Catalytic Sugar-assisted Transfer Hydrogenation with Ru(II), Rh(III) and Ir(III) Halfsandwich Complexes Matthias Böge, AK Heck, Institute of Inorganic and Applied Chemistry, University of Hamburg

13 A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity Florian Schendzielorz, Christian Volkmann,Christian Würtele, Sven Schneider* Institut für Anorganische Chemie, Georg-August-Universität, Tammanstraße 4, Göttingen, Low-valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes, e.g. in the N2 splitting reaction reported by Kunkely and Vogler1 or the partial ammonia production found by Konnick et al.2 However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square-planar osmium(iv) nitride [OsN(PNP)] (PNP = N(CH2CH2PtBu2)2) is reported upon reversible deprotonation of osmium(vi) hydride [Os(N)H(PNP)]+. The OsIV complex shows ambiphilic nitride reactivity with SiMe3Br and PMe3, respectively. Importantly, the hydrogenolysis with H2 gives ammonia and the polyhydride complex [OsH4(HPNP)] in 80% yield. Hence, our results directly demonstrate the role of low-valent osmium nitrides and of heterolytic H2 activation for ammonia synthesis with H2 under basic conditions. Schema 1. Synthesis and reactivity of PNP osmium(iv) nitride complex. 1 2 H Kunkeley, A. Vogler, Angew. Chem. 2010, 122, 1636; Angew. Chem. Int. Ed. 2010, 49, M. M. Konnick, S. M. Bischof, D. H. Ess, R. A. Periana, B. G. Hashiguchi, J. Mol. Catal. A 2014, 382, 1.

14 Group 10 Metal POCOP Fluoride Complexes for Halogen and Hydrogen Bonding Markus Joksch, Anke Spannenberg, Torsten Beweries* Leibniz Institute for Catalysis at the University of Rostock (LIKAT), Albert-EinsteinStraße 29a, D Rostock, Germany, In the field of noncovalent interactions halogen bonding is of increasing interest. Halogens are common constituents of organic and inorganic molecules. The coordination environment determines whether the compound exhibits Lewis acidic or basic character. This leads to two classes of strong, directional intermolecular interactions, referred to as halogen and hydrogen bonding. Structures of this kind have found various applications including coordination and organometallic chemistry, supramolecular chemistry and crystal engineering as well as biochemistry, molecular recognition, topochemical reactions, molecular conductors, and liquid crystals.[2] Transition metal halide complexes are known to participate in hydrogen and halogen interactions.[3] Examples for experimental determination of bonding energies and enthalpies were reported, however, no isostructural series of metal fluorides for direct comparison of ligand and metal influence is known to date.[4] We have synthesized a series of group 10 metal fluoride complexes bearing tridentate POCOP (1,3-bis((di-tert-butylphosphino)oxy)benzene) ligands (Figure 1). The backbone was functionalized (COOMe, tbu) to adjust the electronic properties and investigate the influence on the halogen bonding. All complexes were characterized via NMR, mass spectrometry and X-ray analysis. Figure 1. General scheme of the metal fluoride complexes. [2] [3] [4] M. H. Kolář, P. Hobza, Chem. Rev., Article ASAP, DOI: /acs.chemrev.5b G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimagi, G. Resnati, G. Terraneo, Chem. Rev., Article ASAP, DOI: /acs.chemrev.5b Selected recent examples: a) D. A. Smith, T. Beweries, C. Blasius, N. Jasim, R. Nazir, S. Nazir, C. C. Robertson, A. C. Whitwood, C. A. Hunter, L. Brammer, R. N. Perutz, J. Am. Chem. Soc., 2015, 137, ; b) W. Sattler, S. Ruccolo, G. Parkin, J. Am. Chem. Soc., 2013, 135, ; c) D. A. Smith, L. Brammer, C. A. Hunter, R. N. Perutz, J. Am. Chem. Soc., 2014, 136, ; d) A. Maity, R. J. Stanek, B. L. Anderson, M. Zeller, A. D. Hunter, C. E. Moore, A. L. Rheingold, T. G. Gray, Organometallics, 2015, 34, T. Beweries, L. Brammer, N. A. Jasim, J. E. McGrady, R. N. Perutz, A. C. Whitwood, J. Am. Chem. Soc., 2011, 133,

15 Clustersäuren und Clusterröhren Jonas König, Martin Köckerling* Institut für Chemie, Alber- Einstein-Str. 3A Rostock, Deutschland Durch Entwässerung der Clusterprecursoren [(Nb6Cl12)Cl2(H2O)4] 4H2O mit Thionylchlorid in Gegenwart von organischen Aminobasen ist es uns gelungen wasserfreie, saure Clustersalze der hypothetischen Säure H2[Nb6Cl18] mit 14 Cluster-basierten Elektronen zu synthetisieren. Die Stabilisierung der Clustersäuren gelingt auch durch Koordination der Protonen an Sauerstoffatome von Ethermolekülen. Die Protonen sind in den Etherkomplexen durch jeweils zwei Sauerstoffatome, die einen Abstand von ~2.4 Å aufweisen, koordiniert. Durch Verwendung verschiedener Ether, insbesondere Kronenether, lässt sich eine große Verbindungs-und Strukturvielfalt generieren. Abbildung 1. Struktur eines Ionenpaares der Verbindung [(H-12Krone4)2-µ212Krone4][Nb6Cl18] (Ortep-Plot, 50 % Aufenthaltswahrscheinlichkeit) Interessant ist, dass die Verbindung [H(Et2O)2]2[Nb6Cl18] in Form makroskopischer Röhren von bis zu 2,5 cm Länge und mit einem Durchmesser von 1-2 mm kristallisiert. F. W. Koknat, J. A. Parsons, A. Vongvusharintra, Inorg. Chem. 1974, 13,

16 Applications of N-Heterocyclic Carbene-Phosphinidenes in the Stabilization of Reactive Main-Group and Transition Metal Organometallic Fragments Adinarayana Doddi and Matthias Tamm* Technical University Braunschweig, Hagenring 30, Braunschweig, Germany Phosphinidenes (RP:) are a class of highly reactive low-valent P(I) compounds and are considered as analogues of carbenes (R2C:) and nitrenes (RN:). Free phosphinidenes are only stable at the cryogenic temperatures and in the gas phase. Carbene stabilized phosphinidenes were first time reported by Arduengo et al in In recent times, these ligands have been widely employed both in the main-group and transition metal chemistry. Recently, our group has developed a novel method for the isolation of an N-heterocyclic carbene supported new phosphinidene (IPr=P SiMe3 and IPr=P H) and it was introduced as a synthon for the preparation of terminal carbene phosphinidyne transition metal complexes of the type [(IPr=P)MLn] (MLn=(η6-p-cymene)RuCl and (η5-c5me5)rhcl) (scheme 1). Their spectroscopic and structural characteristics showed their similarities with their arylphosphinidene counterparts.[2] The formally mono negative IPr=P ligand is also capable of bridging two or three metal atoms as demonstrated by the preparation of bi- and trimetallic complexes.[3] Furthermore, several homo and bimetallic coinage metal complexes of carbenephosphinidene adduct (IPr=P Ph) and their respective cationic tetranuclear copper and gold complexes were isolated and structurally characterized.[4] The newly synthesized cationic dual gold complexes were proved to be active catalysts for the cyclo-isomerization of 1,6-enynes and carbene transfer reactions. These findings highlighted the use of carbene-phosphinidenes as promising new ancillary ligands for the homogeneous catalysis. In this presentation, synthetic and bonding aspects of the new main-group [5] and transition metal complexes of formally phosphorus (I) reagents will be discussed in detail. Ln Cl M Cl R N i (i) P i Pr N N Pr i Pr P Me3Si Pr (ii) Rh i N R M = Ru (or) Os; Ln = M= Rh ( or) Ir; Ln = 6 Rh P R N Au Cl N R -p-cymene -Cp* 6 Scheme 1. Synthesis of NHC-phosphinidyne supported terminal and bridging complexes; i) M= Ru and Os (Ln= η6-p-cymene), Rh and Ir (Ln= η6-cp*) and ii) [Rh(COD)Cl]2 (R=2,6-diisopropylphenyl). References (a) A. J. Arduengo, III, J. C. Calabrese, A. H. Cowley, H. V. R. Dias, J. R. Goerlich, W. J. Marshall, B. Riegel, Inorg. Chem. 1997, 36 (10), (b) A. J. Arduengo, III, H. V. R. Dias, J. C. Calabrese, Chem. Lett. 1997, [2] H. Aktaş, J. C. Slootweg, K. Lammertsma, Angew. Chem. Int. Ed. 2010, 49, [3] A. Doddi, D. Bockfeld, T. Bannenberg, P. G. Jones, M. Tamm, Angew. Chem. Int. Ed. 2014, 53, [4] A. Doddi, D. Bockfeld, A. Nasr, T. Bannenberg, P. J. Jones, M. Tamm, Chem. Eur. J. 2015, 21, [5] (a) A. Doddi, D. Bockfeld, P. G. Jones and M. Tamm, Manuscript in preparation. (b) D. Bockfeld, A. Doddi, P. G. Jones and M. Tamm, Eur. J. Inorg. Chem. 2016, ; in press.

17 Speciation Studies and Bond Dissociation Free Energy of Cobalt Complexes with NHPyrazolyl Units Mona Wilken, Merle Kügler und Inke Siewert* Institute for Inorganic Chemistry, Georg-August-University Göttingen, Tammannstr. 4, D Göttingen, Germany, Redox reactions with a high thermodynamic coupling between proton and electron transfer play an important role in biological systems, for example in the oxidative water-splitting at the oxygen evolving centre in photosystem II. This concept has been successfully applied in molecular metal complexes, where the protonation grade of the ligand was shown to have a high influence of the redox properties of the metal ion and vice versa.[2] One possibility to enable different degrees of protonation in the ligand is by introducing NH-units into the ligand backbone. In this context, imidazolyl units in the ligand are known to result in a strong thermodynamic coupling between proton and electron transfer, whereas little is known about similar complexes with pyrazolyl ligands.[3] Scheme 1. Proton coupled electron transfer with imidazolyl/pyrazolyl units. N5-donorligands were shown to create a very stable but also flexible coordination environment for cobalt ions, leaving one coordination site open for the coordination of an anion, solvent molecule or substrate in catalysis.[4] Such a N5-donorligand with four imidazolyl units has been studied previously in our group and was employed as a catalyst for electrochemical water oxidation.[5] An analogue ligand with pyrazolyl moieties and the corresponding cobalt(ii)- and cobalt(iii)-complexes will be presented along with full characterisation and comparison to the previous system. Influence of the imidazolyl vs. pyrazolyl units will be discussed along with potential catalytical applications. T. J. Meyer, M. H. V. Huynh, H. H. Thorp, Angew. Chem. 2007, 119, [2] a) D. R. Weinberg, C. J. Gagliardi, J. F. Hull, C. F. Murphy, C. A. Kent, B. C. Westlake, A. Paul, D. H. Ess, D. G. McCafferty, T. J. Meyer, Chem. Rev. 2012, 112, b) J. J. Warren, T. A. Tronic, J. M. Mayer, Chem. Rev. 2010, 110, [3] a) G. Stupka, L. Gremaud, G. Bernardinelli, A. F. Williams, Dalton Trans. 2004, 407. b) C. Brewer, G. Brewer, C. Luckett, G. S. Marbury, C. Viragh, A. M. Beatty, W. R. Scheidt, Inorg. Chem. 2004, 43, c) F. Lambert, C. Policar, S. Durot, M. Cesario, L. Yuwei, H. Korri-Youssoufi, B. Keita, L. Nadjo, Inorg. Chem. 2004, 43, d) A. Wu, J. Masland, R. D. Swartz, W. Kaminsky, J. M. Mayer, Inorg. Chem. 2007, 46, [4] a) Y. Sun, J. Bigi, N. A. Piro, M. L. Tang, J. R. Long, C. J. Chang, J. Am. Chem. Soc. 2011, 133, b) J. Xie, Q. Zhou, C.Li, W. Wang, Y. Hou, B. Zhang, X. Wang, Chem. Commun. 2014, 50, [5] I. Siewert, J. Gałęzowska, Chem. Eur. J. 2015, 21, 2780.

18 Synthesis and Characterization of Co9-Containing Heteropolyanion Muhammad Qasim, Ali Haider, and Ulrich Kortz* Department of Life Sciences and Chemistry, Jacobs University, P.O. Box , Bremen, Germany. Polyoxometalates (POMs) are soluble metal-oxide clusters with an enormous structural and compositional diversity, and associated physicochemical properties.1 Many transition metalcontaining POMs are known, and our group has also prepared several examples of highnuclearity 3d transition metal-containing POMs with fascinating structures and interesting magnetic, electrochemical and catalytic properties.2 As a continuation of our work on cobalt(ii)-containing POMs with applications in catalysis and magnetism, we have now succeeded in synthesizing the Co9-containing polyanion {Co9Ge3W27}. This compound was characterized in the solid state by single-crystal XRD, infrared spectroscopy, thermogravimetric and elemental analyses. It was also shown that the polyanion {Co9Ge3W27} has attractive magnetic, electrochemical, and catalytic properties. 1. Pope, M. T.; Kortz, U. Polyoxometalates. In Encyclopedia of Inorganic and Bioinorganic Chemistry; R. A. Scott, Ed.; John Wiley: Chichester, a) Haider, A.; Ibrahim, M.; Bassil, B. S.; Carey, A.M.; Nguyen Viet, A.; Xing, X.; Ayass, W. W.; Miñambres, J. F.; Liu, R.; Zhang, G.; Keita, B.; Mereacre, V.; Powell, A. K.; Balinski, K.; N Diaye, A. T.; Kuepper, K.; Chen, H.-Y.; Stimming, U.; Kortz, U. Inorg. Chem. 2016, 55, b) Ibrahim, M.; Haider, A.; Lan, Y.; Bassil, B. S.; Carey, A. M.; Liu, R.; Zhang, G.; Keita, B.; Li, W.; Kostakis, G. E.; Powell, A. K.; Kortz, U. Inorg. Chem. 2014, 53, c) Ibrahim, M.; Lan, Y.; Bassil, B. S.; Xiang, Y.; Suchopar, A.; Powell, A. K.; Kortz, U. Angew. Chem. Int. Ed. 2011, 50,

19 Continuous flow synthesis of Zr-MOFs with UiO-66 framework structure leading to high space time and real time yields Steve Waitschat, Helge Reinsch und Norbert Stock* Christian-Albrechts Universität zu Kiel, Institut für Anorganische Chemie, Max-Eyth Straße 2, Kiel, Germany, Metal organic frameworks (MOFs) are compounds with high potential in a series of applications like gas storage, catalysis or heat transformation. One of the most promising series of MOFs is denoted UiO-66 with fundamental composition ([Zr6(O)4(OH)4(BDC-X)6] (X = NH2, COOH, NO2, BDC2- = benzenedicarboxylate).[2] This compound is usually synthesized in DMF under harsh reaction conditions (T 220 C for 24 hours under autogenous pressure).[3] Thus the scale up of this reaction is difficult, which makes the industrial production challenging. Here we present the development of continuous synthesis protocols for four different MOFs with the UiO-66 framework structure. Initially a small two-syringe-pump flow reactor for making UiO-66 based on terephthalic acid (H2BDC) in DMF was developed.4 Subsequently we constructed a new, larger reactor (Fig. 1) and developed for selected products green aqueous syntheses, which could be transferred to continuous flow syntheses of UiO-66-Fum (based on fumaric acid),5 UiO-66-BDC-NH25 and UiO-66-BDC-COOH.6 The products were characterized in detail by powder X-ray diffraction and nitrogen sorption measurements. Yields and properties are consistent over the full reaction time (Tab. 1). Fig 1. Setup of the flow reactor consisting of the Teflon tube reactor placed in a conventional heating oven, a magnetic membrane pump and a stirrer to homogenize the starting slurry. Tab. 1: Comparison of the Yields and the Space Time Yields (STY) of the UiO-66 MOFs. MOF Yield / g h-1 STY / kg m-3 d-1 Ref. UiO-66-BDC UiO-66-Fum UiO-66-BDC-NH UiO-66-BDC-COOH H. Furukawa, K. E. Cordova, M. O Keeffe and O. M. Yaghi, Science, 2013, 341, [2] M. Kim and S. M. Cohen, CrystEngComm, 2012, 14, [3] J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130, [4] S. Waitschat, M. T. Wharmby and N. Stock, Dalton Trans., 2015, 44, [5] H. Reinsch, S. Waitschat, S. Chavan, K.-P. Lillerud and N. Stock, Eur. J. Inorg. Chem., 2016, DOI: /ejic [6] S. Waitschat. D. Fröhlich, H. Reinsch, S. Chavan, S. Henninger, K.-P. Lillerud and N. Stock, manuscrip in preparation.

20 INFLUENCE OF EXACT EXCHANGE ON THE DIRADICAL CHARACTER B. Alexander Voigt and Carmen Herrmann* Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, Germany The diradical character y of a molecule can be used for designing efficient singlet fission molecules. It also correlates with the bond lengths of molecules in the singlet state and with the second hyperpolarizability γ, which influences the nonlinear-optical properties[2]. Therefore, a good theoretical description of the diradical character is desirable. We studied the behavior of the diradical character upon bond dissociation and different exact exchange admixtures in the exchange correlation functional are compared to the results obtained with complete active space self-consistent field electronic structures. For the evaluation of the diradical character proposed by Ramos-Cordoba et al.[3], Mayer s local spin analysis[4], hs 2 ia = Tr(DSA ) Tr(DSA DS) Tr(Ps SA Ps SA ) X 1 1 1X Γi jkl S kia S laj Γi jkl S lia S kaj + Tr(Ps SA )2, + 2 i jkl 2 i jkl 4 (1) which evaluates the local spins hs 2 ia using the first-order reduced density matrix D, the cumulant of the second-order reduced density matrix Γ, the spin density matrix Ps and the atomic overlap matrix SA, is needed. A post-processing tool was implemented to extract the needed quantities from quantum chemical calculation output files and to calculate the local spins and diradical characters. T. Minami, S. Ito, M. Nakano, The Journal of Physical Chemistry Letters, 4 (2013) [2] R. Kishi, S. Bonness, K. Yoneda, H. Takahashi, M. Nakano, E. Botek, B. Champagne, T. Kubo, K. Kamada, K. Ohta, T. Tsuneda, The Journal of Chemical Physics, 132 (2010) [3] E. Ramos-Cordoba and P. Salvador, Physical Chemistry Chemical Physics, 16 (2014) [4] E. Ramos-Cordoba, E. Matito, I. Mayer, P. Salvador, Journal of Chemical Theory and Computation, 8 (2012) 1270.

21 Low-temperature NH3-SCR of NO over excellent performing catalysts V2O5/Ce1-xTixO2 studied by operando spectroscopies T. H. Vuong, J. Radnik, J. Rabeah, U. Bentrup, U. Armbruster, A. Brückner,* Leibniz Institute for Catalysis at the University of Rostock, Albert-Einstein-Str. 29a, Rostock, Germany, Selective catalytic reduction (SCR) of nitrogen oxides by ammonia over V2O5-WO3/TiO2 catalysts is an established technology for cleaning of exhaust gases from power plants which, however, operates only in a rather high and narrow temperature range of C. The temperature of other NOx sources such as diesel or lean-burn gasoline engines is much lower. Therefore, SCR catalysts being sufficiently active and selective at low temperature and high space velocities are highly desired. Among the wide variety of catalysts tested in recent years, those based on (modified) ceria belong to the most promising ones due to their oxygen mobility and interesting redox properties[2-4]. This property is promoted even more, when isovalent metal cations of smaller diameter such as Zr4+ or Ti4+ are incorporated in Ce lattice positions. Recently we have shown this for series of V/CexZr1-xO2 catalysts in which almost 100 % NO conversion and N2 selectivity have been reached already around 200 C, without any deactivation during 190 h at a GHSV of 70,000 h-1 which outperformed the state of the art significantly [5]. In the present work, we have explored a series of catalysts containing V2O5 dispersed on mixed CeO2-TiO2 supports, for low-temperature NH3-SCR of NO, since we expected that partial replacement of Ce4+ by smaller Ti4+ ions with a higher redox potential promotes defect formation and oxygen transport within the catalyst lattice and, thus, catalytic activity even more than observed for the corresponding V/CexZr1-xO2 system [5]. The interaction of bare supports and catalysts with individual feed components (NH3, NO+O2) and total NH3-SCR feed was investigated by operando EPR, DRIFTS and pseudo-in situ XPS to elucidate redox behaviour and mechanistic details. V/Ce0.5Ti0.5O2 was most active and selective, showing 100% NO conversion to N2 at 190 C with a GHSV of 70,000 h-1 (Fig. 1). Besides high surface area, both high amount of acid sites as well as fast and reversible VOx redox cycles revealed to be essential for active catalysts. The NH3-SCR over free-v supports followed a Langmuir-Hinshelwood mechanism while an Eley-Rideal mechanism is highly probable for V-containing catalysts. In the best catalyst V/Ce0.5Ti0.5O2, EPR data suggest that active VOx sites are effectively connected to the support surface, probably within O Ce O V(=O) O Ti O moieties, which may support oxygen transport and the redox behaviour of the V sites. Fig. 1. Catalytic behaviour of Ce1-xTixO2 supports and V/Ce1-xTixO2 catalysts References J. Li, H. Chang, L. Ma, J. Hao, R.T. Yang, Catal. Today, 2011, 175, [2] C. Li, Q. Li, P. Lu, H. Cui, G. Zeng, Front. Environ. Sci. Engin., 2012, 6, [3] Z. Lian, F. Liu, H. He, Catal. Sci. Technol., 2015, 5, [4] Y. Peng, C. Wang, J. Li, Appl. Catal., B, 2014, 144, [5] T.H. Vuong, J. Radnik, E. Kondratenko, M. Schneider, U. Armbruster, A. Brückner, Appl. Catal., B, 2016, in press.

22 Synthesis and characterization of visible light photocatalytic active Bi2WO6 coated TiO2 inverse opals Michael Teck, Thorsten M. Gesing* Institut für Anorganische Chemie und Kristallographie, Universität Bremen,, Leobener Straße /NW2, Bremen With the discovery of the photocatalytic splitting of water on TiO2 electrodes in 1972 by Fujishimna and Honda, the use of irradiated semiconductors for photocatalysis has been the subject of intensive studies [2]. Most of the used TiO2 in this field consist of the commercial product Degussa P25 and its irradiation with light in the UV-region - the area of its electronic band gap and therefore the limited photocatalytic usability of the material. A possible way to overcome this limitation might lay in the quite new scientific field of photonic crystals [3], by revealing new pathways to increase the photon-efficiency with the use of the so called slow photons. First attempts to prove this pure morphological adaptivity with the already visiblelight driven photocatalyst Bi2WO6 were already carried out by Zhang et al. [4] to prove this concept of enhancement. Herein we extended this idea by synthesizing a new photocatalytic active composite material by producing photonic crystals made of TiO2 (Fig. 1) and coating their surface with Bi2WO6. This enables to use low energy visible light photons together with the high energy UV photons both on the Bi2WO6 layer and the non-absorbed higher penetrating layer one in the TiO2 framework. We then exploited the position of the calculated photonic band gap to tune the morphology of the inverse opal structure and hereby to achieve an overlap with the electronic band gap of the Bi2WO6 and maximize its photon-efficiency. This higher activity could be successfully verified through the degradation of rhodamine B using a light source limited to the visible region of light. Figure 1: Schematic production process for the TiO2 inverse opal structure using polymer spheres as template. A. Fujishima, K. Honda, Nature,1972,37, 238. [2] H. Kisch, Angew. Chemie - Int. Ed., 2013, 52, 812. [3] E. Yablonovitch, Phys. Rev. Lett., 1987, 58, 2059 [4] L. Zhang, C. Baumanis, L. Robben, T. Kandiel, D. Bahnemann, Small, 2011, 7, 2714.

23 Cooperative assembly synthesis of mesoporous SrTiO3 with enhanced photocatalytic activity Bugra Kayaalp,,[a] Youngjoo Lee,[a] Andreas Kornowsky,[b] Silvia Gross,[c] Simone Mascotto,*[a] [a] Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-LutherKing Platz 6, Hamburg, Germany [b] Institut für Physikalische Chemie, Universität Hamburg, Grindelallee 117, Hamburg, Germany [c] Istituto per l Energetica e le Interfasi, IENI-CNR and INSTM, UdR Padova, via Marzolo, 1, I-35131, Padova, Italy * JProf. Dr. Simone Mascotto simone.mascotto@chemie.uni-hamurg.de Keywords: (perovskite oxide, mesoporous SrTiO3, photocatalysis) The synthesis of mesoporous SrTiO3 combining Pechini method and silica hard templating is presented here. The high affinity and intimate mixing between the TEOS precursor and the metal chelating agents fostered the cooperative assembly of the corresponding inorganic and organic polymer [2]. Hence, after calcination and removal of the siliceous phase, highly porous SrTiO3 with interconnected, well defined pores and crystalline pore walls was obtained. Systems with different SrTiO3:SiO2 molar ratios were prepared. At low concentrations of template, only monomeric and oligomeric domains of silica could be formed. Conversely, significant condensation of the siloxane groups and formation of dense domains occurred for concentrations larger than 20%. The porous properties of the final perovskite reproduce the structural evolution of the silica in the nanocomposite materials very well. Only at high concentrations the condensed silica species acted as real template leading to the formation of large surface areas (SBET = 240 m2/g) with defined pore sizes. Finally, the activity of the mesoporous SrTiO3 systems was demonstrated by exemplary photodegradation tests of methylene blue. The dye conversion progressively increased with the content of silica template up to 7 times than for the corresponding non-porous system, as result of the combined increase of porosity and decrease of crystallite size. M. Kakihana, T. Okubo, M. Arima, Y. Nakamura, M.Yashima and M. Yoshimura, J. Sol-Gel Sci. Technol. 1998, 12, [2] Y. Deng, T. Yu, Y. Wan, Y. Shi, Y. Meng, D. Gu, L. Zhang, Y. Huang, C. Liu, X. Wu and D. Zhao, J. Am. Chem. Soc. 2007, 129,

24 Deliquescence behavior of NaCl confined in nanopores Tanya Talreja, Kirsten Linnow und Michael Steiger* Fachbereich Chemie, Universität Hamburg Deliquescence behavior of salts confined in pores smaller than 100 nm is no more equivalent to that of bulk crystals. It is strongly affected by the curvature of the liquid-vapor interface, when the pore size of the porous material gets smaller than 100 nm. One of the consequences of the curved interface is the decrease in pressure in the liquid phase, leading to a decrease in the solubility of the salt crystals. Contrary to that, it has been shown in previous studies that there is an increase in solubility with decreasing crystal size.[2] The competitive influences of the reduced pressure and the crystal size on the solubility partly compensate each other leading to a mild change in solubilities of salts in small pores. However, in contrast to the solubilities, the deliquescence humidity of a salt confined in small pore decreases significantly with decreasing pore size. To our knowlwdge, experimental investigations about the influence of confinement below 100 nm in diameter on the deliquescence humidity of a salt are not yet carried out. The present work provides the results of the water sorption measurements of different NaClsilica-composites with pores smaller than 100 nm carried out to investigate the deliquescence behavior of confined NaCl. The experimental results revealed a significant decrease of the deliquescence humidity (DRH) with decreasing pore size. The calculations of the sorption behavior of NaCl confined in the respective pore sizes, based on combined use of the YoungLaplace equation, the Kelvin equation and the Pitzer ion-interaction model, matches well with the experimental results. According to the calculations, the main reason for the decrease of the relative vapor pressure over the salt solution in the unsaturated pore is the concave curvature of the liquid-vapor interface Fig. 1. Pore size dependent DRH for confined NaCl. The blue line indicates the calculated predictions and the red squares are the experimental results of the water sorption measurements. M. Steiger, K. Linnow in Final Report on Priority Program Funded by DFG (Eds.: L. Franke, G. Deckelmann, R. Espinosa-Marzal), Cuvillier-Verlag, Göttingen, 2009, pp [2] M. Steiger, Crystal growth in porous materials-ii: Influence of crystal size on the crystallization pressure, J. Cryst. Growth 2005, 282,

25 Spin switchable Ni(II) salpn-complexes for functional MRI contrast agents Hannah Brandenburg, F. Tuczek* Institute for Inorganic Chemistry, Christian-Albrechts-University Kiel, Max-Eyth-Str. 2, Kiel, Germany, The first magnetically bistable system in solution at room temperature was published by 2011 by Herges et al. Spin-state-switching in this so-called recordplayer has been achieved by a reversible change of the coordination number of a nickel(ii)porphyrin complex, i.e. through a conversion from the square-planar low spin state to the square-pyramidal high spin state. Since the change of the coordination sphere is caused by the photoisomerization of an azopyridine ligand that can only bind in its cis configuration, this effect has been termed lightdriven coordination-induced spin state switching (LD-CISSS).[1,2] A simpler version of this effect has also been evidenced for nickel(ii)porphyrins coordinated by photodissociable ligands (PDLs). These ligands which are, e.g. substituted azopyridines, bind in their trans configuration and will dissociate when switched to the cis configuration.[3] It appeared of interest to us to achieve the LD-CISSS effect also with other, non-porphyrin ligand-based systems forming the equatorial coordination environment. In our approach the porphyrin is exchanged by salicylideneiminate derivatives. Scheme 1. Coordination-induced spin state switching with Ni(II) salpn-complexes. Hence novel Ni(II) model complexes based on salicylideneiminate ligands with various substituents were synthesized and characterized. To induce the association of an azopyridine to the nickel center such as in a LD-CISSS system, pyridine was titrated to the model complexes and the change of the spin state was monitored by Evans-NMR experiments. Association constants at different temperatures were determined and thermodynamic parameters (ΔH, ΔS) were evaluated. S. Venkataramani, U. Jana, M. Dommaschk, F.D. Sönnichsen, F. Tuczek, R. Herges, Science 2011, 331, 445. [2] M. Dommaschk, C. Schütt, S. Venkataramani, U. Jana, C. Näther, F. D. Sönnichsen, R. Herges, Dalton Trans. 2014, 43, [3] S. Thies, H. Sell, C. Bornholdt, C. Schütt, F. Köhler, F. Tuczek, R. Herges, Chem. Eur. J. 2012, 18,

26 Activation of 7-Silanorbornadienes by N-Heterocyclic Carbenes A Selective Way to NHC-Stabilized Silylenes Dennis Lutters, Claudia Severin, Marc Schmidtmann, Thomas Müller* Institute of Chemistry, Carl von Ossietzky University of Oldenburg, Carl von Ossietzky-Str. 911, Oldenburg, Federal Republic of Germany 7-Silanorbornadienes such as 2[1,2] are known to be a source of silylenes by thermolysis and photolysis.[3] Characteristics for these species are the unusual deshielded 29Si NMR resonances (δ29si = 98 32) and elongated Si C bonds (Si C: pm) due to β-sic hyperconjugation between the strained Si C bonds and the C=C double bonds.[4,5] A closer look at the front orbitals of 7-silanorbornadiene 1 shows that the LUMO is mainly located at the silicon atom and is of antibonding character in respect of both strained Si C bonds. An electron donation into this orbital by an extern electron donor like N-heterocyclic carbene 3 should weaken these Si C bonds further and finally lead to the fragmentation of the 7-silanorbornadiene into the silylene and the aromatic leaving group (Scheme 1).[6] The experimental verification of this hypothesis will be described. A theoretical assessment of the scope and limitations of this reaction suggests that it is general and can be used also for the synthesis of other carbene analogues such as germylenes and phosphinidenes.[7] Scheme 1. 7-Silanorbornadiene 1, calculated surface diagram of the LUMO of 1 (at M062X/6-311+G(d,p), iso density value 0.035) and the fragmentation reaction of 7silanorbornadiene 2 with N-heterocyclic carbene 3 to give NHC-stabilized hydridosilylene 4. Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl, Ter* = 2,6-bis(2,4,6-triiso-propylphenyl)phenyl. T. Sasamori, S. Ozaki, N. Tokitoh, Chem. Lett. 2007, 36, 588. [2] C. Gerdes, W. Saak, D. Haase, T. Müller, J. Am. Chem. Soc. 2013, 135, [3] For recent summary, see M. Okimoto, A. Kawachi, Y. Yamamoto, J. Organomet. Chem. 2009, 694, [4] C. Gerdes, J. Schuppan, A.-R. Grimmer, M. Bolte, W. Saak, D. Haase, T. Müller, Silicon 2011, 2, 217. [5] H. Sakurai, Y. Nakadaira, T. Koyama, H. Sakaba, Chem. Lett. 1983, 12, 213. [6] For related process, see A. Sekiguchi, M. Ichinohe, S. Yamaguchi, J. Am. Chem. Soc. 1999, 121, [7] D. Lutters, C. Severin, M. Schmidtmann, T. Müller, J. Am. Chem. Soc (ASAP, DOI: /jacs.6b02824).

27 Kupplungsfähige Fluoroionophore Für die Detektion von Kalium- und Natrium-Ionen im Lysosom Tobias Sprenger, Thomas Schwarze und Hans-Jürgen Holdt* Anorganische Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, Potsdam, Deutschland, Alkalimetall-Ionen besitzen in vielen biologischen Prozessen eine bedeutende Rolle, weshalb eine Kenntnis über die Konzentrationsverhältnisse und Konzentrationsverteilungen innerhalb lebender Zellen und Zellkompartimente von Interesse ist. Eine viel genutzte Möglichkeit zur Detektion von Ionen ist die Fluoreszenzspektroskopie unter Verwendung geeigneter Fluoroionophore. Aufgrund des niedrigen ph-wertes innerhalb des Lysosoms ( ) ist die Zahl der geeigneten Fluoroionophore eingeschränkt, da weder die Rezeptoreinheit noch das Fluorophor über protonierbare Strukturelemente verfügen dürfen. Deshalb können die häufig genutzten Aza-Kronenether und Triaza-Kryptanden als selektive Rezeptoreinheiten nicht verwendet werden. Abbildung 1: Kupplungsfähige Fluoreszenzfarbstoffe für die Detektion von Natrium- und Kalium-Ionen im Lysosom. Wir favorisieren für die Na+- und K+-Detektion im Lysosom ph-unabhängige Fluoroionophore mit Coumarino- (1) oder Benzokronenether-Rezeptoreinheiten (2). 1 und 2 werden mit Carboxylgruppen funktionalisiert, um Konjugate mit Aminodextran generieren zu können. Während die Coumarino-Fluoroionophore 1 die Detektion von Alkalimetall-Ionen durch Fluoreszenzlöschung ermöglichen, kann mit den Benzokronenether-BODIPYFluoreszenzfarbstoffen 2 eine Na+- bzw. K+-Bestimmung durch Fluoreszenzanstieg erfolgen. S. Weinert, S. Jabs, C. Supanchart, M. Schweizer, N. Gimber, M. Richter, J. Rademann, T. Stauber, U. Kornak, T. J. Jentsch, Science 2010, 328,

28 Synthesis of circular P-N-P containing ligands Martha Höhne, Bernd H. Müller and Uwe Rosenthal* Leibniz Institute for Catalysis at the University of Rostock (LIKAT), Albert-EinsteinStraße 29a, D Rostock, German, From a synthetic point of view, the chemistry of phosphorus is challenging and does not always follow the predicted routes. A common product class are phosphorus compounds containing nitrogen. Established P-N-P ligands such as diphosphinoamines are well known and investigated. Open chained N-P-N-P-N compounds as ligands of chromium complexes prove to be excellent in catalysis of selective oligomerization of ethylene.[2] However annular P-N-P containing compounds are less attended and with regard to their catalytic potential as ligands barely examined. We developed selective syntheses of circular P-N-P ligands either by varying and optimizing the reduction of dihalogenated P-N-P fragments or via nucleophilic substitution with hydrazine derivatives (Scheme 1). Scheme 1. Syntheses of different P-N-P containing ring systems. Consequently the preparation of innovative ring shaped P-N-P compounds succeeded, which could find application as potential ligands in coordination chemistry and homogeneous catalysis. First exploratory studies of the coordination chemistry of selected P-N-P containing ring systems with chromium and molybdenum sources were undertaken and exhibit interesting coordination behavior. M.- S. Balakrishna, V. S. Reddy, S. S. Krishnamurthy, J. F. Nixon, J. Laurent, S. Burckett, Coord. Chem. Rev. 1994, 129, [2] N. Peulecke, B. H. Müller, A. Spannenberg, M. Höhne, U. Rosenthal, A. Wöhl, W. Müller, A. Alqahtani, M. Al Hazmi, Dalton Trans. 2016, 45,

29 Intramolecular Lewis-Pairs Felix Kutter, Enno Lork and Jens Beckmann* Universität Bremen, Institut für anorganische Chemie und Kristallographie, Leobener Str., Bremen, Germany Lewis-Pairs can show promising results in metal-free catalysis1. Recent examples also include intramolecular compounds, which react differently depending on intramolecular distance2,3. We introduce a series of mainly silicon-phosphorus compounds of different composition. Figure 1. Lewisstructure of the molecules. Our main focus is the synthesis of different ligand systems and their dimethylsilanephosphorus-derivates, as well as their behaviour towards acids, bases, and consecutive small molecule activation. D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 2010, 49, [2] Z. Mo, E. L. Kolychev, A. Rit, J. Campos, H. Niu, S. Aldridge, Organometallics 2015, 137, [3] T. Komuro, T. Arai, K. Kikuchi, H. Tobita, Organometallics 2015, 34,

30 Investigating the bonding situation in main-group element oxygen bonds Malte Fugel, Lorraine A. Malaspina, Rumpa Pal, Florian Kleemiß, Simon Grabowsky* Institut für Anorganische Chemie und Kristallographie, Universität Bremen, Fachbereich 2, Leobener Straße NW2, Bremen The Lewis picture poses a very powerful description of the bonding situation in molecules, but it does not come without its limitations: For some molecules containing atoms of the third period or higher, various Lewis formulas that either exceed or follow the octet rule exist (e.g. the sulfate anion). The possible Lewis formulas for the perchlorate anion are depicted in Figure 1. The hypervalent formula 1 is often perceived to be the predominant one, whereas formula 3, which is the only one to follow the octet rule, is considered more unlikely due to high formal charges[2]. The theoretical and experimental charge density studies (multipole model[3] and X-ray constraint wavefunction fitting[4]) conducted in this project aim to shed light on the bonding situation of the phosphate, sulfate and perchlorate anion. Figure 1. Left: Possible Lewis formulas for the perchlorate anion. Right: Laplacian isosurface of the perchlorate anion. The results of these studies conclusively validate the non-hypervalent Lewis formulas to be of the greatest importance. Four equivalent polarized single bonds and three lone pairs at each of the four oxygen atoms are suggested by the analysis of the natural bond orbitals [5], the topology of the electron density (Bader analysis)[6], the Laplacian of the electron density and the electron localizibilty indicator[7]. The existence of three oxygen lone pairs of the perchlorate anion can be clearly visualized by the Laplacian iso-surface shown in Figure 1. In addition to these three anions, localized X-O single bonds, where X is an element of the second and third period, are investigated in a similar way as explained above. The model compounds, for which ab-initio calculations were performed are chosen so that X and O are saturated with hydrogen atoms (HnXOH) in order to obtain localized X-O single bonds. The analyses suggest four categories that the bonds can be assigned to: ionic bonds (Li-O, Be-O, Na-O and Mg-O), highly polarized covalent bonds (B-O, Al-O, Si-O), polarized covalent bonds (C-O, N-O, S-O, Cl-O) and charge shift bonds[8] (O-O, F-O). M. S. Schmøkel, S. Cendense, M. R. V. Jørgensen, Y.-S. Chen, C. Gatti, D. Stalke, B. B. Iversen, Inorg. Chem. 2012, 54, [2] G. Wulfsberg, in Inorganic chemistry, University Science Books, Sausalito, 2000, 115. [3] N. K. Hansen, P. Coppens, Acta Cryst A 1978, 34, [4] S. C. Capelli, H.-B. Bürgi, B. Dittrich, S. Grabowsky, D. Jayatilaka, IUCrJ 2014, 1, [5] J. K. Badenhoop, F. Weinhold, J. Chem. Phys. 1997, 107, [6] R. W. F. Bader, Chem. Rev. 1991, 91, [7] M. Kohout, Int. J. Quantum Chem. 2003, 97, [8] S. Shaik, D. Danovich, B. Silvi, D. L. Lauvergnat, P. C. Hiberty Chem. Eur. J. 2005, 11,

31 Isolation of labile pseudohalogen species NSO René Labbow,a Dirk Michalik,b Fabian Reiß,b Axel Schulz,*a,b and Alexander Villingera a Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-EinsteinStraße 3a, Rostock, Deutschland b Leibniz-Institut für Katalyse e.v. an der Universität Rostock, Albert-Einstein-Straße 29a, Rostock, Deutschland rene.labbow@uni-rostock.de, axel.schulz@uni-rostock.de With a new synthetic approach, highly labile thionylimide, H NSO, was generated, trapped by adduct formation with the bulky Lewis acid B(C6F5)3 and fully characterized (Figure 1, left). For comparison, a series of different Me3Si NSO[2] Lewis acid adducts was studied. Treatment of Me3Si NSO with the silylium ion [Me3Si]+ led to the formation of the hitherto unknown iminosulfonium ion [Me3Si N=S O SiMe3]+ (Figure 1, right) that could be isolated and fully characterized as salt in the presence of weakly coordinating carborate anions. S O N B H C F Figure 1. ORTEP representation of the B(C6F5)3 adduct of H NSO (left) and the homoleptic silylated [3] [Me3Si NSO SiMe3][CHB11Cl11] (right). We will report of Lewis acid assisted isomerisation of the silylated sulfinylamine to a siloxathiazate. Our investigations refer to reactions using different classical Lewis acids like gallium trichloride, GaCl3, or the more sterically demanding tris(pentafluorophenyl)borane, B(C6F5)3, as well as highly reactive species like the trimethylsilyl cation, [Me3Si]+. In this manner, different Lewis acids led on different pathways to the formation of a diversity of structural isomers. a) F. Ephraim, H. Piotrowski, Chem. Ber. 1911, 44, ; b) P. Günther, R. Meyer, F. MüllerSkjøld, Z. Phys. Chem. A 1935, 175, [2] a) O. J. Scherer, P. Hornig, Angew. Chem. 1966, 16, ; b) K. I. Gobbato, C. O. Della Védova, H. Oberhammer, J. Mol. Struct. 1995, 350, [3] R. Labbow, D. Michalik, F. Reiß, A. Schulz, A. Villinger, Angew. Chem. 2016, /anie

32 C H-Aktivierung sekundärer Amine Ausbildung von Titanacyclen und deren Folgechemie Manfred Manßen, Nicolai Lauterbach, Marc Schmidtmann, Rüdiger Beckhaus* Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Straße 911, Oldenburg, Deutschland, Kenntnisse über C H-Aktivierungs- und C H-Eliminierungsreaktionen in der Koordinationssphäre früher Übergangsmetalle haben wesentlich zum Verständnis der Reaktivität metallorganischer Verbindungen beigetragen.[1,2] In aktuellen Forschungsansätzen wird die Umwandlung von sekundären Aminen in die jeweiligen Imine bzw. Azadiene, ausgehend von Allylaminen, betrachtet. Diese titanvermittelte Reaktion ist von beeindruckendem akademischem und industriellem Interesse. Niedervalente Komplexverbindungen des Titans zeigen, dass sie sehr gut für die Ausbildung vielfältiger Metallacyclen geeignet sind. Bei Verwendung von Bis( 5, 1-pentafulventitan)komplexen laufen simultane N H- und C H-Aktivierungsreaktionen unter Bildung von Metallaziridinen bzw.-azabutadienkomplexen ab.[3] Aufgrund der ausgebildeten Ti CH2-Gruppe sind diese Komplexe in der Lage eine Vielzahl von Folgereaktionen einzugehen. Hier sind beispielhaft die Insertionen von Mehrfachbindungssubstraten mit einhergehender ungewöhnlicher Ringerweiterung zu nennen (siehe Abb. für Azabutadienkomplexe). Alle erhaltenen neuen Verbindungen wurden umfassend, einschließlich der Einkristallstrukturuntersuchungen, charakterisiert. W. Scherer, D. J. Wolstenholme, V. Herz, G. Eickerling, A. Brück, P. Benndorf, P. W. Roesky, Angew. Chem. Int. Ed. 2010, 49, [2] W. A. Nugent, D. W. Ovenall, S.J. Holmes, Organometallics 1983, 2, [3] M. Manßen, N. Lauterbach, J. Dörfler, M. Schmidtmann, W. Saak, S. Doye, R. Beckhaus, Angew. Chem. Int. Ed. 2015, 54,

33 NH activation of ammonia by Rhodium complexes containing diphosphines Moritz Horstmann, Wolfgang Baumann und Detlef Heller* Leibniz Institut für Katalyse, Albert-Einstein-Straße 29a, Rostock, Germany The direct hydroamination of alkenes with ammonia is known as one of the most challenging goals in catalysis for more than 20 years. The cleavage of the NH-bond (ammonia activation) under formation of amido complexes is discussed to be a key step to realize this reaction. Various types of metal complexes have been proved to be able to activate ammonia.[2] Oro et al. published the formation of amido complexes of Rhodium for the first time starting from diolefin complexes.[3] We investigated complexes of Rhodium containing diphosphines (PP) in the context of ammonia activation and found the first successful examples of these complex species. Schema 1. Reactions of Rhodium complexes containing diphosphines with ammonia. The cationic complexes [Rh(PP)(diolefin)]+ or [Rh(PP)(solvent)2]+ leads in presence of ammonia to the diammin complex [Rh(PP)(NH3)2]+. We could confirm that the substitution of the diolefin by gaseous ammonia is also possible in solvent free reactions.[4] Furthermore we found that the methoxy-bridged complexes [Rh(µ2-OMe)(PP)]2 and also [Rh3(µ3anion)2(PP)3]+ react with ammonia under formation of dinuclear amido complexes [Rh(µ2NH2)(PP)]2 (PP = dipamp, diop, dppe, binap). To prove this structure the same complex has been generated both by addition of base (e.g. NaH or NatBuO) to the diammin complex [Rh(PP)(NH3)2]+ and by adding NaNH2 to the solvate complex [Rh(PP)(solvate)2]+.[5] The complexes have been characterized by NMR spectroscopy (1H, 15N, 31P, 103Rh) and in case of PP = binap also by a crystal structure of the amido complex. J. Haggin, Chem. Eng. News 1993, 71, [2] J. I. van der Vlugt, Chem. Soc. Rev. 2010, 39, [3] I. Mena, M. A. Casado, P. Garcia-Orduna, V. Polo, F. J. Lahoz, A. Fazal, L. A. Oro, Angew. Chem. Int. Ed. 2011, 50, ; Angew. Chem. 2011, 123, [4] S. D. Pike, T. Kramer, N. H. Rees, S. A. MacGregor, A. S. Weller, Organometallics 2015, 34, [5] A. Preetz, C. Kohrt, A. Meissner, S. Wei, H.-J. Drexler, H. Buschmann, D. Heller, Catal. Sci. Technol. 2013, 3,

34 Synthesis and Coordination Chemistry of new α-oxygen Substituted Alkyne Complexes Christopher Timmermann, Julia Rüger, Kai Helmdach, Alexander Villinger and Wolfram W. Seidel* University of Rostock, Albert-Einstein-Straße 3a, Rostock Alkynes with two donor atoms, such as P, N, S, O and Se in α-position are well suited as ligands which can coordinate transition metals in the favoured η2-c,c -binding mode. Oxygen substituted alkynes, who prefer the side-on coordination are known as alcoholic derivates or stabilized by lewis-acid/base adducts.[2] Therefore the synthetic strategies and the preparation of alkynes with N or P in α-position[3] were adapted for ethoxyacetylene to generate O,N- and O,P-system which were coordinated at a tungsten precursor. Both systems have been completely characterized. O N C1 C2 C1 W C2 W O P Cl 4 (R= Ph) 7 Schema 1.: Synthesis of the O,N- and O,P-system including molecular structures of the products 4 (R = Ph) and 7 (Tp = tris(3,5-dimethyl-1-pyrazolyl)borate; Tp* = tris(3,4,5trimethyl-1-pyrazolyl)borate) The synthesis of the alkyne complexes 4 and 7 and the different pitfalls, that had to be circumvented, will be presented. Insights in the electronic structures and the metal ligand delocalization are based on spectroscopic investigates like Raman, Infrared, NMR and X-ray. Finally, the potential use of 4 as a κ2-p,o-chelate ligand will be discussed. R. N. Vrtis, C. P. Rao, S. G. Bott, S. J. Lippard, J. Am. Chem. Soc., 1988, 110(22), [2] M. R. Churchill, H. J. Wasserman, S. J. Holmes, R. R. Schrock, Organometallics, 1982, 1(5), [3] W. W. Seidel, J. Rüger, Ch. Timmermann, A. Villinger, A. Hinz, D. Hollmann, Chem. Eur. J., 2016, DOI: /chem

35 Synthesis of pyrazine-pyrane-dithiolene complexes mimicing specific features of the molybdenum cofactor (MoCo) C. Schindler, C. Schulzke* Institut für Biochemie, Ernst-Moritz-Arndt Universität Greifswald, Felix-Hausdorff-Strasse 4, Greifswald, Deutschland, Molybdopterin (MPT) dependent enzymes are part of nearly any known organism on earth ranging from ancient archaea over plants to modern human beings. While the biological synthesis of MPT is well understood, a chemical synthetic pathway is very challenging and is still being studied. The aim of the project is the synthesis of model compounds for the molybdopterin depending cofactor, which are able to catalyse oxygen atom transfer reactions and which can be incorporated into the apoenzyme. The focus of our research is the development of ligand precursors that address the dithiolene function, the pyrane ring and the adjacent pyrazine ring and their coordination with especially molybdenum to understand the influence of various structural units on the stability, the catalytic properties or the redox potential. Simultaneously we also explore models in which the pyrazine is replaced by a quinone. While still being able to engage in hydrogen bonding the quinone would be even better with respect to electron transfer. Financial support of the European Research Council is gratefully acknowledged. O O O H N NH H2N S N Mo S L1 OH L2 S S L1 L2 molybdenum cofactor N H O O O P HO OH OH quinone model compounds O H N Mo S O Mo S L1 O L2 S Mo S L1 L2 target model compound N H O O L1, L2 = O, OR, SR Literature: [2] [3] [4] Ben Bradshaw, Andrew Dinsmore, David Collison, C. David Garner, John A. Joule, J. Chem. Soc., Perkin Trans. 1, 2001, Edward C. Taylor, Reinhard Dötzer, J. Org. Chem., No. 5, Ulf Ryde, Carola Schulzke, Kerstin Starke, J. Biol. Inorg. Chem., 2009, Claudia Schindler, Carola Schulzke, Chemistry of Heterocyclic Compounds, 2015, 51(11/12),

36 P-MOFs with Potentially Coordinating Secondary Sites Timo Stein, Frank Hoffmann, and Michael Fröba* Institute of Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, Germany Phosphorus-functionalized Metal-Organic Frameworks (P-MOFs) offer promising opportunities as solid ligands for transition metals, thus potentially allowing for catalytic applications or tuning of host-guest interactions.[2] We are preparing new phosphorus-functionalized linker molecules suitable for the synthesis of P-MOFs that feature organic units derived from ligand motifs wellknown from coordination chemistry. The tetratopic linker molecule [1,1 :3,1 -terphenyl]-2 -dimethylphosphoryl3,3,5,5 -tetracarboxylic acid (1) and its phosphane sulfide derivative 2 (see Fig. 1) consist of the m-terphenyl backbone bearing dimethylphosphoryl or dimethylthiofig. 1: The tetratopic phosphorusphosphoryl functionalities attached to the central arene, substituted linker molecules 1 5. respectively. 1 and 2 were reacted with Cu(II) salts under solvothermal conditions to yield isostructural UHM-60 (UHM: University of Hamburg Materials) and UHM-61, respectively. Topologically, these MOFs can be described by the rare ucp net.[3] UHM-60 and UHM-61 are thermally stable up to 200 C and feature permanent porosity (N2 BET surface areas of 1940 m2g-1 and 1930 m2g-1, respectively). As the phosphorus functional groups within UHM-60 and UHM-61 show only limited accessibility towards post-synthetic metalation reactions, our target was to obtain more open structures with regard to the secondary coordinating sites. Sterically more demanding organic substituents were attached to the phosphorus atom of the linker molecule 1 to obtain its 2 diethylphosphoryl (3) and 2 -diphenylphosphoryl derivatives (4). Solvothermal syntheses with Cu(II) salts resulted in isostructural materials UHM-62 and UHM-63, respectively, that could be characterized by single crystal X-ray diffraction. Possible topological descriptions include that of a tetranodal (3,4)-c net previously also found for PCN-88.[4] A highly polar pore might render UHM-62 and UHM-63 interesting in terms of coordination chemistry, studies of magnetic interactions, or gas storage/separation. UHM-63 shows permanent porosity (N2 BET surface area of 1358 m2g-1) and is stable up to 280 C. In order to synthesize P-MOFs bearing soft Lewis donor sites, the 2 -diphenylphosphinosubstituted linker molecule 5 was reacted with Cd(II) and Mg(II) salts to give UHM-70 and UHM-80, respectively, both of which were characterized by single crystal X-ray diffraction. Interestingly, the P(III) functionality remained intact for UHM-70 during solvothermal synthesis, while for UHM-80, partial oxidation at the phosphorus site was observed. UHM-70 shows a new topology, while UHM-80 exhibits fog topology.[3] J. Václavík, M. Servalli, C. Lothschütz, J. Szlachetko, M. Ranocchiari, J. A. van Bokhoven, ChemCatChem 2013, 5, [2] A. J. Nuñez, L. N. Shear, N. Dahal, I. A. Ibarra, J. Yoon, Y. K. Hwang, J.-S. Chang, S. M. Humphrey, Chem. Commun. 2011, 47, [3] M. O Keeffe, M. A. Peskov, S. J. Ramsden, O. M. Yaghi, Acc. Chem. Res. 2008, 41, [4] J.-R. Li, J. Yu, W. Lu, L.-B. Sun, J. Sculley, P. B. Balbuena, H.-C. Zhou, Nat. Commun. 2013, 4, 1538.

37 Catalytic Sugar-assisted Transfer Hydrogenation with Ru(II), Rh(III) and Ir(III) Halfsandwich Complexes Matthias Böge, Philip Saul, Jürgen Heck* Hamburg University, Martin-Luther-King-Platz 6, Hamburg Halfsandwich ruthenium(ii), rhodium(iii) and iridium(iii) complexes of methyl 2,3-diamino4,6-O-benzylidene-2,3-dideoxy-α-D-hexopyranoside ligands have been applied in asymmetric transfer hydrogenation of acetophenone in 2-propanol and display the highest enantiomeric excesses in the class of catalyst precursors with ligands containing two coordinating amino groups. The configuration of the hexopyranosides and the type of arene ligands determine the formation of R- or S-1-phenylethanol up to 66 % ee despite the presence of two mirrored catalytic sites. A large influence of the substitution pattern of the arene ligands on the extent of the enantiomeric excess is demonstrated. The D-gluco- and D-mannopyranoside ligands behave as pseudo-enantiomers in asymmetric transfer hydrogenation. + O O BF4- O 1 mol% O OMe Ar = p-cymene, tetralin H2N NH2 gluco: [T-4-S] manno: [T-4-R]/[T-4-S] Ru Cl Ar OH 5 mol% KO-tBu 2-propanol 5 % in 2-propanol < 66 % ee DFT calculations allowed the identification of the favored transition states in transfer hydrogenation of acetophenone and revealed a site differentiation of the (pseudo)-trigonal deactivated catalyst in the formation of the diastereomeric active catalysts, which are (pseudo)-tetrahedral hydrido complexes. Related studies concerning the epimerization of the compounds will eventually be discussed. M. Böge, J. Heck, J. Mol. Catal. A. 2015, 408,

38 Posterprogramm Posternummer P1 Titel und Autor Magnetismus & Stabilität von Bisamidophosphankobalt(II) Komplexen Jan Gerkens, AG Schneider, Georg-August-Universität Göttingen P2 P3 P4 Crystallization studies of perovskite oxides confined in nanopores Jonas Scholz, AG Mascotto, Universität Hamburg The Synthesis and Reactivity of A Homoaromatic Germylene Zhaown Dong, AG Müller, Carl von Ossietzky University of Oldenburg Co-ligand-dependent formation of three new porphyrin based CeMOFs Timo Rhauderwiek, AG Stock, Christian-Albrechts Universität, Kiel P5 Reaktion von Pentafulvenmetallkomplexen mit Phosphoryliden Ylide als intramolekulare Protonenshuttles Tim Oswald, AG Beckhaus, Carl von Ossietzky Universität Oldenburg P6 Rhenium(I) and Manganese(I) Complexes with Amino- and IminoPyridine Ligands Metal-Ligand Cooperation as Key for an Unusual CO2 Binding-Mode Rasmus Stichauer, AG Vogt, Universität Bremen P7 P8 Highly K+-Selective Fluorescent Probes Thomas Schwarze, AG Holdt, Universität Potsdam Photochemical and structural studies of substituted (diphenylthiophosphoryl)anthracene derivatives Timo Schillmöller, AG Stalke, Georg-August-University Göttingen P9 P10 The Reaction Pathway of Neutral Dinuclear Rhodium(I) Precatalysts Saskia Moeller, AG Heller, Leibniz-Institute for Catalysis (LIKAT), Rostock Activation of Dioxygen Using Dinuclear Ir(I)-Complexes Wiebke Dammann, AG Burger, Universität Hamburg

39 P11 P12 P13 P14 New Derivatives of Trinuclear 1,6,7,12,13,18Hexaazatrinaphthylene Titanium Complexes Pia Fangmann, AG Beckhaus, Carl von Ossietzky Universität, Oldenburg Low Valent Osmium PNP Pincer Complexes Josh Abbenseth, AG Schneider, Georg-August-Universität Göttingen Synthese und Reaktivität von Bis( 5; 1-benzofulven)titan komplexen Malte Fischer, AG Beckhaus, Carl von Ossietzky Universität Oldenburg, Tunable, Redox-Active Diphos Ligands with a Metal-ComplexBackbone Stephan Ludwig, AG Seidel, Universität Rostock P15 Novel chelate ligands for stabilization of low-valent group 13 metal centres Johannes Kretsch, AG Stalke, Georg-August-University Goettingen P16 P17 Mes*2NP3Cl2 A novel P3N ring system? Jonas Bresien, AG Schulz, Universität Rostock Melting temperatures and solubilities of Zn(NO3)2 6H2O nanocrystalsconfined in mesoporous materials Tobias Grünzel, AG Steiger, Universität Hamburg P18 Chromium and Titanium Phenoxy-Pyridine-type Complexes for the Polymerisation and Co-polymerisation of Olefins Jia-Pei Du, AG Siewert, Georg-August-Universität Göttingen P19 Untersuchung von peri-substituierten Phosphonium-SiliciumAcenaphthen- Verbindungen Sebastian Holsten, AG Beckmann, Universität Bremen P20 Die erste Niob-Clusterverbindung mit gleichzeitig innen-außen verknüpfenden Liganden: [Nb6(OC2H4NH2)6I-A(OC2H4NH2)6I]I3, Synthese und Charakterisierung Daniel Holger Weiß, AG Köckerling, Universität Rostock P21 Synthese neuartiger Vanadium(IV/V)-Katalysatoren für die enantioselektive Oxidation von prochiralen Sulfiden Lina Fischer, AG Schulzke, Universität Greifswald P22 Ligand centered radical reactivity of a Ni(III) PNP Pincer Complex Felix Schneck, AG Schneider, Georg-August Universität Göttingen

40 Iron catalyzed dehydropolymerization of methylamine borane P23 P24 Felix Anke, AG Beweries, Leibniz-Institut für Katalyse, Universität Rostock Photo-Switchable Electromeric Complexes Bearing Dithienylethene Ligand Motifs Controllable Redox NonInnocence Induced by External Stimuli in a V(IV) Complex Dirk Schlüter, AG Vogt, Universität Bremen P25 Artaios a transport code for post-processing quantum chemical electronic structure calculations Michael Deffner, AG Herrmann, Universität Hamburg P26 P27 Introducing Thallium in Polyoxometalate Chemistry Wassim W. Ayass, AG Kortz, JacobsUniversität Bremen Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Achiral Dipyrrinato Ligand Julius F. Kögel, Universität Bremen P28 Donor- und Akzeptor-funktionalisierte 2,2'-Bipyridin- und 2Phenylpyridin-komplexe als Chromophore für die nichtlineare Optik Marie Christine Wolff, Sebastian Triller; AG Heck, Universität Hamburg P29 P30 Phosphorstabilisierte Boreniumionen Sinas Furan, AG Beckmann, Universität Bremen Towards precise and accurate determination of hydrogen atom positions with X-ray diffraction data utilizing hydrogen maleate salts Lorraine A. Malaspina, AG Grabowsky, Universität Bremen P31 Development of Ni and Co catalysts for the (co-)polymerization of olefins and polar monomers and hydrofunctionalization of olefins Andreea Enachi, AG Walter, TU Braunschweig P32 Flüssige Eisen-Schwefel-Cluster Neue Elektrolyte für Redox-Flow-Batterien Christian Modrzynski, AG Burger, Universität Hamburg P33 Activation and Coupling Studies of Pyridin-Diimin-Complexes with Dioxygen Max Völker, AG Burger, Universität Hamburg

41 P34 Temperature-dependent investigation of Na8(MO4) [AlSiO4]6 (M = Cr, Mo, W) cancrinites Hilke Petersen, AG Gesing, Universität Bremen P35 PNP Fe complexes as selective and highly active catalysts for dehydrogenation of hydrazine borane Delong Han, AG Beweries, (LIKAT) Rostock P36 Synthese und Charakterisierung neuer Molybdän-DistickstoffKomplexe mit linearen tridentaten PEP-Liganden (E = P, N) Katharina Grund, AG Tuczek, Christian-Albrechts Universität, Kiel P37 GDCh Jungchemiker

42 Magnetismus & Stabilität von Bisamidophosphankobalt(II) Komplexen Jan Gerkens, Christian Volkmann, Christian Würtele und Sven Schneider* Georg-August-Universität Göttingen, Institut für Anorganische Chemie Tammannstraße 4, Göttingen Bisamide des Kobalts sind seit den Pionierarbeiten von Bürger und Wannagat aus den 60er Jahren bekannt. In den letzten Jahren ist das Interesse an dieser Substanzklasse aufgrund der magnetischen Eigenschaften als Einzelmolekülmagnete wieder gestiegen.[2-3] Power und Mitarbeiter berichteten erstmalig die strukturelle Charakterisierung des Kobalt(II)amids [Co{N(SiMe3)2}2(THF)] (3) und deren magnetische Untersuchung.[2] Wir präsentieren hier eine Serie von neuen Bisamidophosphancobalt(II) Komplexen mit unterschiedlich substituierten Phosphanen und Amiden (1, 2, 4). Der Einfluss der Liganden auf die magnetischen Eigenschaften und die thermische Stabilität wird diskutiert. Schema 1. Darstellung verschiedener Bisamidokobalt(II) Komplexe. [2] [3] H. Bürger, U. Wanngat, Monatsh. Chem. 1963, A. M. Bryan, G. J. Long, F. Grandjean, P. P. Power, Inorg. Chem. 2013, 52, A. fer,y. Lan, V. Mereacre, T. Bodenstein, F. Weigend, Inorg. Chem. 2014, 53,

43 Crystallization studies of perovskite oxides confined in nanopores Jonas Scholz,[a] Youngjoo Lee,[a] Andreas Meyer[b], Simone Mascotto,*[a] [a] Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-LutherKing Platz 6, Hamburg, Germany [b] Institut für Physikalische Chemie, Universität Hamburg, Grindelallee 117, Hamburg, Germany * JProf. Dr. Simone Mascotto simone.mascotto@chemie.uni-hamurg.de Keywords: (perovskite oxide, crystallization, nanoconfinement) Perovskite oxides are considered a very versatile class of materials suitable for a wide range of applications. However, the poor textural properties still limit their functionality. One general strategy to increase their active surface area is to use nanoporous silica either as host matrix to disperse perovskite nanoparticles or as a mould for the complete structural replication, i.e., nanocasting. In both cases, the silica is initially impregnated with the perovskite precursor solution and subsequently treated at high temperature to promote the crystallization of the guest species. However, the formation of crystalline perovskite phase within the pores is not a straightforward process. In the present work we systematically addressed the crystallization of several distorted perovskite structures (LaFeO3, LaCoO3, PrFeO3) in silica matrices with different pore sizes and arrangements. Interestingly, crystal growth occurred only in spherical pores of 12 nm or less, organized in a Fm3m structure (Figure 1). Combining spectroscopic, diffraction and thermal analyses, important insights into the crystallization mechanism of perovskites in nanopores could be achieved. Figure 1: LaFeO3 crystallized in different porous silica hosts

44 The Synthesis and Reactivity of A Homoaromatic Germylene Zhaowen Dong, Crispin R. W. Reinhold, Thomas Müller * Carl von Ossietzky University of Oldenburg, Institute of Chemistry, Carl von Ossietzky Straße 9-11, D Oldenburg, Federal Republic of Germany zhaowen.dong@uni-oldenburg.de Germole dianions have attracted chemists attention because of their electronic properties, potential aromaticity and their high reactivity. The reactivity of silole dianions has been investigated by the group of West,[2] nevertheless, there are only a few reports about the reactivity of germole dianions. Here we report the synthesis of the homoaromatic germylene 2 and the first reactivity studies via dipotassio germolediide 1 reacting with Cp2HfCl2 (Figure 1). Figure 1. The synthesis and reactivity of a homoaromatic germylene 2 Acknowledgements: This work was supported by the Carl von Ossietzky University Oldenburg. Z.W. Dong thanks the Ministry of Science and Culture (MWK) of the Lower Saxony State for a Georg-Lichtenberg scholarship. a) J. H. Hong, Y. L. Pan, P. Boudjouk, Angew. Chem. Int. Ed. Engl., 1996, 35, b) S. B. Choi, P. Boudjouk, J. H. Hong, Organometallics, 1999, 18, c) S. B. Choi, P. Boudjouk, K. Qin, Organometallics, 2000, 19, d) Y. X. Liu, D. Ballweg, T. Müller, L. A. Guzei, R. W. Clark, R. West, J. Am. Chem. Soc., 2002, 124, [2] a) I. S. Toulokhonova, T. C. Stringfellow, S. A. Ivanov, A. Masunov, R. West, J. Am. Chem. Soc., 2003, 125, b) I. S. Toulokhonova, I. A. Guzei, R. West, J. Am. Chem. Soc., 2004, 126, c) I. S. Toulokhonova, V. I. Timokhin, D. N. Bunck, I. Guzei, R. West, T. Müller, Eur. J. Inorg. Chem., 2008,

45 Co-ligand-dependent formation of three new porphyrin based Ce-MOFs Timo Rhauderwiek, Norbert Stock* Institute of Inorganic Chemistry, Christian-Albrechts University, Kiel/Germany The modular structure of Metal Organic Frameworks (MOFs) allows one to tune the pore size and pore surface properties, which in turn leads to a large range of chemical and physical properties.[1-3] Hence MOFs are investigated in applications such as gas storage and separation, drug delivery or catalysis. The most important challenge for the application of MOFs in photo-catalysis is a high redox potential of the metal and/or the linker.[4] Porphyrinbased linker molecules in combination with redox active cerium ions could be a promising combination due to a possible synergetic redox potential and a resulting high photo-catalytic activity.[5] 4-Tetracarboxyphenylporphyrine (H6TCPP) is the most intensively investigated porphyrin-linker in MOF synthesis,[6] but only few porphyrin based MOFs are known with cerium in the inorganic building unit.[7] [8] Herein we present the synthesis and characterization of three new porphyrin based Ce-MOFs, CAU-18, [Ce4(H2TCPP)3(DMF)2(H2O)4], CAU-19-H (-2Cl, -4NH2, -3CO2), [Ce3(H2TCPP)2(C7H5O2)2(H2O)2] and Ce-PMOF-4NO2, [Ce2(H2TCPP)(C7H4O2NO2)2]. The formation of the respective MOFs depends mainly on the carboxylic acid used in the synthesis as a co-ligand. The structures of CAU-18 and -19 were determined from single crystal X-ray diffraction data. CAU-18 (Fig. 1) is synthesized in the absence of an additive. CAU-19 can be synthesized with different benzoate derivatives (unfunctionalized (-H), 2-chloro- (-2Cl), 4amino- (-4NH2) and 3-carboxyl-benzoate (-3CO2). The compounds CAU-19-X (X=-H, -2Cl, 4NH2, -3CO2) are porous towards N2 and exhibit specific surface areas between 300 and 600 m2 g-1, depending on the functional group X. Ce-PMOF is obtained in the presence of 4nitrobenzoic acid as the co-ligand. Surprisingly, in organic solvents a full phase transformation into CAU-19-4NO2 takes place. Schema 1. Graphical representation of the structures of CAU-18 (left) and CAU-19-H (right). The individual inorganic building unit is shown left and a view along the pores of both MOFs is shown on the right, respectively. H. Furukawa, K. E. Cordova, M. O Keeffe, O. M. Yaghi, Science 2013, 341. [2] N. Stock, H. Reinsch, L.-H. Schilling, in Metal Organic Frameworks as Heterogeneous Catalysts, The Royal Society of Chemistry, 2013, pp [3] H.-C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, [4] Z. Guo, B. Chen, Dalton Trans. 2015, 44, [5] C.-W. Kung, T.-H. Chang, L.-Y. Chou, J. T. Hupp, O. K. Farha, K.-C. Ho, Chem. Commun. 2015, 51, [6] W.-Y. Gao, M. Chrzanowski, S. Ma, Chem. Soc. Rev. 2014, 43, [7] S. Lipstman, I. Goldberg, J. Mol. Struct. 2008, 890, [8] S. Lipstman, S. Muniappan, S. George, I. Goldberg, Dalton Trans. 2007,

46 Reaktion von Pentafulvenmetallkomplexen mit Phosphoryliden Ylide als intramolekulare Protonenshuttles Tim Oswald, Marc Schmidtmann, Rüdiger Beckhaus* Institut für Chemie, Carl von Ossietzky Universität Oldenburg, D Oldenburg, Deutschland, Pentafulvenkomplexe der frühen Übergangsmetalle haben sich aufgrund der erfolgten Umpolung sowie des Ausbleibens kinetischer Hemmungen als vielseitige Synthesebausteine erwiesen.[1-4] Die Reaktion der Bis( 5: 1-pentafulven)titankomplexe Ti1a und Ti1b mit Phosphoryliden führt zu einer raschen CH-Aktivierung der Methyleneinheit unter milden Bedingungen und liefert die Produkte Ti2a-e in guten Ausbeuten. Durch Verwendung eines Mono( 5: 1-pentafulven)titankomplexes Ti3 kann zusätzlich zu der CH-Aktivierung ein katalytisch reversibler H-Transfer durch das Phosphorylid beobachtet werden. Dieses dient als intramolekulares Protonenshuttle, der zugrunde liegende Prozess konnte anhand spektrochemischer Untersuchungen aufgeklärt werden. Zusätzlich wurde die Reaktivität des neugebildeten Pentafulvenliganden in Ti4b im Hinblick auf bekannte Reaktionsmuster in unserem Arbeitskreis untersucht. [2] [3] [4] H. Ebert, V. Timmermann, T. Oswald, W. Saak, M. Schmidtmann, M. Friedemann, D. Haase, R. Beckhaus, Organometallics 2014, 33, M. Diekmann, G. Bockstiegel, A. Lützen, M. Friedemann, D. Haase, W. Saak, R. Beckhaus, Organometallics 2006, 25, 339. A. Scherer, S. Fürmeier, D. Haase, W. Saak, R. Beckhaus, A. Meetsma, M. W. Bouwkamp, Organometallics 2009, 28, M. Manßen, N. Lauterbach, J. Dörfler, M. Schmidtmann, W. Saak, S. Doye, R. Beckhaus, Angewandte Chemie 2015, 127, 4458.

47 Rhenium(I) and Manganese(I) Complexes with Amino- and Imino-Pyridine Ligands Metal-Ligand Cooperation as Key for an Unusual CO2 Binding-Mode Rasmus&Stichauer,&Jennifer&Bremer,&Arne&Helmers,&Tunay&Tüfek,&Andre&Wark,&Markus&Rohdenburg,& Christian&Rugen,&Wiebke&Wohltmann,&Fabian&Schmitt,&Sarah&Matz,&Enno&Lork,&and&Matthias&Vogt*& University&of&Bremen,&Institute&of&Inorganic&Chemistry&and&Crystallography,&Leobener&Str.,&28359& Utilization of CO2 as a sustainable C1 source to produce chemical commodities is a topic with growing importance.1,2 Naturally, catalytic conversion of CO2, triggered by a homogeneous catalyst, requires the initial binding of the CO2 molecule to the catalyst prior to its chemical transformation. The binding of CO2 to a metal center commonly proceeds via π-coordination of a C=O bond or formation of a σ -bond to the carbon atom (σ-coordination through the O atom is rare). Alternative CO2 binding modes including the participation of the ligand, became recently an active field of research.3-6 We report Re(I) and Mn(I) compounds with simple-touse 2-amino- and 2-iminomethyl-pyridine ligands (ampy1 5 and impy1 5), serving as metalligand cooperative scaffolds. fac-[m(ampy1 5)(CO)3Br] compounds (11 5) are prepared by stirring the specific amino-pyridine ligand (ampy1-5) and [M(CO)5Br] (M= Re or Mn) in toluene or ethanol at elevated temperatures. Upon addition of excess base (LiHMDS) the complexes are doubly deprotonated to give the anionic complexes Li[Re(amidopy*)(CO)3] (31 5, the asterisk indicates double-deprotonation). 3a1-5 rapidly react with CO2 under C C and M O bond formation to form the [1,3]-addition product Li[M(amidopy1-5 COO)(CO)3] (4a1 5). The CO2 binding is triggered by re-aromatization of the pyridine moiety. Remarkably, substitution experiments involving 13C-labelled 13CO2 suggest a reversible binding of CO2. Alternatively, the related complexes fac-[m(impy1-5)(co)3br] (21 5), which are prepared similarly, can be reduced in THF solutions with potassium to give [K][Re(amidopy1-5*)(CO)3] (3b1 5). Complexes 3b1 5 readily react with CO2 to form the corresponding complexes [K][Re(amidopy1-5 COO)(CO)3] (4b1-5). We are currently investigating the reactivity of the [1,3]-addition products. Preliminary experiments suggest N and O methylation of complex 4b4 M= Re upon addition of MeI to form fac-[re(ampy4-nme COOMe)(CO)3]I (A1). O R1 5 N Br N M CO CO CO ; For M = Re and R3 Mab= K K THF d8, RT DMSO air, T M=Re N CO2 thf, T R THF d8, RT O R1 R2 Br CO 11 5 M= R3 R4 F Re N OMe N Me Re Re Mn Mn Mn Re Re Mn OC OTf R R5 F R1 5 = CO CO 4a1 5 Mab=Li 4b1 5 Mab=K Me O NH M CO CO 3a1 5 Mab=Li 3b1 5 Mab=K CO R1 5 N M MeOTf MabOTf CH2Cl2 M CO LiHMDS N OC Mab+ CO N R N CO2 thf, 1 bar 21 5 Mab+ O M CO Me CO (A1) Schaub, T.; Paciello, R. A. Angew. Chem. Int. Ed. 2011, 50, [2] Quadrelli, E. A.; Centi, G.; Duplan, J.L.; Perathoner, S. ChemSusChem 2011, 4, [3] Vogt, M.; Gargir, M.; Iron, M. A.; Diskin-Posner, Y.; BenDavid, Y.; Milstein, D. Chem.-Eur. J. 2012, 18, [4] Sgro, M. J.; Stephan, D. W. Chem. Commun. 2013, 49, [5] Huff, C. A.; Kampf, J. W.; Sanford, M. S. Organometallics 2012, 31, [6] Annibale, V. T.; Song, D. Chem. Commun. (Camb.) 2012, 48, 5416.

48 Highly K+-Selective Fluorescent Probes Thomas Schwarze and Hans-Jürgen Holdt* Anorganische Chemie, Universität Potsdam, Karl Liebknecht Straße 24-25, Potsdam, Deutschland, There is a tremendous demand for highly K+-selective probes to monitor and visualize the top analyte K+ in life science. We develop, in the field of bioanalytical and biomedical research, new fluorescent probes for K+, see Scheme 1. These fluorescent probes allow the determination of K+ by an enhancement of the fluorescence intensity at one wavelength (cf. Scheme 1, fluorescent probes 1, 2 and 5)[1,2,3] or by changes of fluorescence emissions at two wavelengths (see probe 4). Further, we design fluorescent probes for K+ by fluorescence lifetime changes to apply these K+-probes in fluorescence lifetime imaging microscopy (FLIM) experiments (cf. Scheme 1, probe 6).[4] In addition to it, we synthesize two-photon fluorescent dyes for K+ to visualize K+ in vitro and in vivo (see probe 3).[5] Overall, these probes are based on newly developed signal transduction chains and are able to be modified in terms of the dissociation constant (Kd) value, the solubility, the emission spectrum as well as the two-photon cross-section. The Scheme 1 shows highly K+/Na+ selective fluorescent probes 1-6. Probes 1 and 2 allow a K+ determination by K+-induced fluorescence enhancements (FE) by a factor of 2.5 at 493 nm. The two-photon excited fluorescence (TPEF) probe 3 shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mm K+, independently of one-photon (OP, 430 nm) or two-photon (TP, 860 nm) excitation. 4 is a ratiometric fluorescent probe for K+ with a dual emission at 405 nm and 505 nm. K+ reduces the emission at 505 nm and enhances the fluorescence intensity at 405 nm. Probe 5 shows even in the presence of Na+ ions equal Kd values (Kd = 45 mm) and equal K+induced fluorescence enhancement factors (FEFs = 2.3). Thus, the fluorescent probe 5 showed an outstanding K+/Na+ selectivity. Finally, the fluorescent probe 6 reveals a K+induced FEF of 2.8 and a decay time enhancement from 17 ns to 22 ns. Thus, the fluorescent probe 6 is a suitable fluorescent tool to measure extracellular K+ levels by fluorescence lifetime changes. Scheme 1. Highly K+/Na+-selective fluorescent probes 1-6. [2] [3] [4] S. Ast, H. Müller, R. Flehr, T. Klamroth, B. Walz, H.-J. Holdt, Chem. Commun. 2011, 47, S. Ast, T. Schwarze, H. Müller, A. Sukhanov, S. Michaelis, J. Wegener, O. S. Wolfbeis, T. Körzdörfer, A. Dürkop, H.-J. Holdt, Chem. Eur. J. 2013, 19, T. Schwarze, R. Schneider, J. Riemer and H.-J. Holdt, Chem. Asian J. 2016, 11, 241. P. Wessig, M. Mertens, J. Riemer, T. Schwarze and H.-J. Holdt, in preparation. [5] T. Schwarze, J. Riemer, S. Eidner and H.-Jürgen Holdt, Chem. Eur. J. 2015, 21,

49 Photochemical and structural studies of substituted (diphenylthiophosphoryl)anthracene derivatives Timo Schillmöller, Dietmar Stalke* Institute for Inorganic Chemistry,Georg-August-University Göttingen, Tammannstraße 4, Göttingen, Lower Saxony, Germany Anthracene derivatives are important compounds in the development of luminescent materials both in solution and in the solid state. While the dynamic processes and electronic effects that dominate luminescence properties in solution are well understood[2], only little information on the underlying mechanisms behind the solid-state fluorescence is available.[3] Fei et al. reported a symmetric substituted 9,10-bis(diphenylthiophosphoryl)anthracene which exhibits strong solid-state fluorescence upon excimer formation with co-crystallized toluene.[4] We now present five asymmetric 9,10-substituted (diphenylthiophosphoryl)anthracene derivatives with varying substituents in the 10-position (Scheme 1). Scheme 1. Synthesized and investigated asymmetric (diphenylthiophosphoryl)anthracene derivatives 1-5 (left) and their solid-state emission spectra (right). By selective variation of the substituents in the 10-position we want to find explanations of their photochemical properties by understanding their respective packing motif. Indeed, the derivatives 3, 4 and 5 show strong solid-state emission, whereas 1 and 2 are only weakly fluorescent (Scheme 1). In addition, the photochemical properties in the solid-state are compared to in-solution experiments. (a) E. J. Bowen, E. Mikiewicz, Nature, 1947, 159, 706; (b) W. H. Wright, Chem. Rev. 1967, 67, 581. [2] (a) J F. Callan, A. P. de Siva, D. C. Magrim, Tetrahedon 2005, 51, 8551; (b) J. Wu, W. Liu, J. Ge, H. Zhang, P. Wang, Chem. Soc. Rev. 2011, 40, [3] (a) H. Langhals, T. Potrawa, H. Nöth, G. Linti, Angew. Chem. Int. Ed. 1989, 28, 478; (b) A. Drew, J. Plötner, L. Lorenz, J. Wachtveitl, J. E. Djanhan, J. Brüning, T. Metz, M. Bolte, M.U. Schmidt, Angew. Chem. Int. Ed. 2005, 44, [4] Z. Fei, N. Kocher, C.J. Mohrschladt, H. Ihmels, D. Stalke, Angew. Chem. Int. Ed. 2003, 42, 783.

50 The Reaction Pathway of Neutral Dinuclear Rhodium(I) Pre-catalysts Saskia Moeller, Hans-Joachim Drexler and Detlef Heller*, Leibniz-Institute for Catalysis (LIKAT), Albert-Einstein Straße 29a, Rostock, Germany Dinuclear rhodium(i) complexes are widely used in homogenous catalysis, for example, in selective CO gas-free hydroformylations, propargylic CH activations[2] and antimarkovnikov additions of carboxylic acids to terminal alkynes[3]. A detailed knowledge about deactivation processes is of general importance to maximize the profitable usage of the mostly expensive catalysts in corresponding reactions. It has to be emphasized that deactivation phenomena can already occur during the usually used in situ formation of the pre-catalyst. For this purpose our research is focused on the formation and reactivity of neutral dinuclear rhodium(i) diphosphine complexes of the type [{Rh(diphosphine)(µ2-Cl)}2].[4,5] These pre-catalysts are generated by the reaction of a diphosphine ligand with a dinuclear rhodium(i) precursor that contains two µ2 bridging ligands and two terminal diolefins. Crystallographic and detailed spectroscopic investigations will be presented for complexes based on the diphosphine ligand DPEPhos (figure). With respect to our previously published results according to the symmetric pre-catalyst [{Rh(diphosphine)(µ2-Cl)}2] and the unsymmetric intermediate [Rh2(diphosphine)(COD)(µ2-Cl)2] we were able to prove these postulates by crystallization experiments.[4] Thereby an additional symmetic intermediate crystallized. The structure revealed a non-chelating coordination mode of the diphosphine ligand DPEPhos. This unexpected ligand rearrangement redefines the question according to the coordinative bond strength between rhodium(i) and diphosphine ligands. The interrelationship of these two intermediates will be described. G. Makado, T. Morimoto, Y. Sugimoto, K. Tsutsumi, N. Kagawa, K. Kakiuchi. Adv. Synth. Catal., 2010, 352, [2] U. Gellrich, A. Meissner, A. Steffani, M. Kahny, H. J. Drexler, D. Heller, D. A. Plattner, B. Breit. J. Am. Chem. Soc., 2014, 136, [3] S. Wei, J. Pedroni, A. Meissner, A. Lumbroso, H.-J. Drexler, D. Heller, B. Breit. Chem. Eur. J., 2013, 19, [4] A. Meissner, A. Preetz, H.-J. Drexler, W. Baumann, A. Spannenberg, A. Koenig, D. Heller. ChemPlusChem, 2015, 80, [5] A. Meissner, A. Koenig, H.-J. Drexler, R. Thede, W. Baumann, D. Heller. Chem. Eur. J., 2014, 20,

51 Activation of Dioxygen Using Dinuclear Ir(I)-Complexes Wiebke Dammann and P. Burger* University of Hamburg, Martin-Luther-King-Platz 6, Hamburg One important goal of catalytic chemistry is the selective oxidation of organic substrates using dioxygen. Both the functionalisation of complex organic molecules and the selective aerobic oxidation of methane to methanol are under scientific investigation. The activation of oxygenoxygen bonds in late transition metal complexes is a focus of quite a few research groups. It is well established that cooperative effects can facilitate the activation of small molecules. For reaction of dinuclear copper complexes with molecular oxygen the correlation of metal metal distance and oxygen binding mode is known. In this work the reactivity of dinuclear iridium(i) complexes towards dioxygen is studied. We are focussing on cooperative effects and the influence of the iridium-iridium distance on the oxygen binding mode. The synthesis, reactivity and crystal structure of di-iridium systems with a defined metalmetal distance will be reported. Reaction of anthra[ir(me6n3)cl]2. C. He, J. L. Dubois, B. Hedman, K. O. Hodgson, S. J. Lippard Angew. Chem. Int. Ed. 2001, 40,

52 New Derivatives of Trinuclear 1,6,7,12,13,18-Hexaazatrinaphthylene Titanium Complexes Pia Fangmann, Marc Schmidtmann, Rüdiger Beckhaus* Institute of Pure and Applied Chemistry, Carl von Ossietzky University P.O. Box 2503, D Oldenburg The trischelating nitrogen heterocyclic molecule 1,4,5,8,9,12- hexaazatriphenylene (HAT) and its homologues, for example 1,6,7,12,13,18-hexaazatrinaphthylene (HATN) or its hexamethyl derivative (HATNMe6) were often studied in the context of their coordination modes to metal ions, photophysical properties, liquid crystalline ordering, lightharvesting systems and chirality[1,2]. In our group the (Cp2Ti)3HATNMe6-complex[3] is known but bad soluble and shows a very interesting electronic structure, e.g. the electrochemistry (6 oxidations and 2 reductions)[4] and antiferromagnetic coupling between the metal centers. The synthesis of new (better soluble) derivatives should give an in-depth look into this type of trinuclear complexes. The replacement of methyl-groups to phenyl-groups was the first step to increase the solubility. In such a way, an optimized synthetic procedure for 1 was developed. With the synthesis of this new HATNPh6-Titanium-complex 2 we have now a good soluble complex for further investigations. The solid state structure and interesting aspects of the electrochemistry, UV/Vis/NIR-spectra and magnetic properties are discussed. [2] [3] [4] S. Kitagawa, S. Masaoka Coord. Chem. Rev. 2003, 246, J. L. Segura, R. Juarez, M. Ramos, C. Seoane Chem. Soc. Rev. 2015, 44, I. M. Piglosiewicz, R. Beckhaus, W. Saak, D. Haase, J. Am. Chem. Soc. 2005, 127, I. M. Piglosiewicz, R. Beckhaus, G. Wittstock, W. Saak, D. Haase, Inorg. Chem. 2007, 46,

53 Low Valent Osmium PNP Pincer Complexes Josh Abbensetha, Sarah Betea, Christian Würtelea, Sven Schneidera* a Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, Göttingen Square-planar low valent osmium complexes remain an scarcely characterized class of compounds due to the limited number of isolated examples. The utilization of an unsaturated aliphatic PNP-pincer ligand allows for the preparation and structural characterization of the highly reactive square-planar complex [OsCl{N(CHCHPtBu2)2}]. Spectroscopic and computational characterization suggests a triplet ground state. This complex provides an excellent platform for the synthesis of electron-rich, low-valent osmium complexes, such as osmium(iv) nitride [OsN{N(CHCHPtBu2)2}]. Scheme 1. Synthesis of the low-valent OsII-Platform including follow up reactions. a) Anhaus, J.T.; Kee, T.P.; Schofield M.H.; Schrock R.R., J. Am. Chem. Soc. 1990, 112, b) Esteruelas, M. A.; Modrego F. J.; Onate E.; Royo E., J. Am. Chem. Soc. 2003, 125, c) Tsvetkov, N; Pink M.; Hongjun F.; Joo-Ho L.; Caulton K.G., Eur. J. Inorg. Chem. 2011, 40,

54 Synthese und Reaktivität von Bis( 5; 1-benzofulven)titankomplexen Malte Fischer, Kerstin Fitschen, Marc Schmidtmann, Rüdiger Beckhaus* Institut für Chemie, Carl von Ossietzky Universität Oldenburg, D Oldenburg, Deutschland, Bis( 5; 1-pentafulven)komplexen der Gruppe 4 haben sich aufgrund der Umpolung des exocyclischen Kohlenstoffatoms als hervorragende Ausgangsverbindungen für eine Vielzahl von Folgereaktionen wie Element H-Aktivierungensreaktionen erwiesen.[1-4] Hier berichten wir über die Nutzung prochiraler Benzofulvenliganden, welche die Möglichkeit eröffnen Bis( 5; 1-benzofulven)titankomplexe diastereoselektiv, in hohen Ausbeuten und unter milden Reaktionsbedingungen zu erhalten. In angeschlossenen Reaktivitätsstudien zeigten sich die Verbindungen 2a und 2b als äußerst reaktiv gegenüber einer Vielzahl von Substraten. Während die Umsetzung von Bis( 5; 1-pentafulven)komplexen mit geeigneten sekundäre Aminen unter doppelter Element H-Aktivierung zu Titanaaziridinen führt, reagieren die Komplexe 2a und 2b mit Dibenzylamin entgegen den Erwartungen zu den Titanaazapentacylen 3a und 3b. Neben dieser Reaktion unter gleichzeitiger N H- und C H-Aktivierung werden zahlreiche weitere Folgereaktionen vorgestellt. Sämtliche Reaktionen verlaufen hoch substratspezifisch, selektiv und quantitativ ab. Weiterhin ist besonders die Herstellung diastereomerenreiner Verbindungen bei Insertionsreaktionen hervorzuheben. [2] [3] [4] M. Manßen, N. Lauterbach, J. Dörfler, M. Schmidtmann, W. Saak, S. Doye, R. Beckhaus, Angew. Chem. Int. Ed. 2015, 54, 4383; Angew. Chem. 2015, 127, H. Ebert, V. Timmermann, T. Oswald, W. Saak, M. Schmidtmann, M. Friedemann, D. Haase, R. Beckhaus, Organometallics 2014, 33, A. Scherer, S. Fürmeier, D. Haase, W. Saak, R. Beckhaus, A. Meetsma, M. W. Bouwkamp, Organometallics 2009, 28, M. Diekmann, G. Bockstiegel, A. Lützen, M. Friedemann, D. Haase, W. Saak, R. Beckhaus, Organometallics 2006, 25, 339.

55 Tunable, Redox-Active Diphos Ligands with a Metal-Complex-Backbone Stephan Ludwig, Kai Helmdach, Alexander Villinger and Wolfram W. Seidel* Universität Rostock, Institut für Chemie, Albert-Einstein-Straße 3a, Rostock In asymmetric catalysis, diphos ligands such as BINAP, exhibiting intrinsic chirality are well established. Redox active diphos ligands, however, are restricted to 1,1'-Bis(diphenylphosphino)ferrocene (dppf) and its derivatives. Accordingly, ligands combining both chirality and redox-acticity are particularly rare and even those few compounds of that type in use today, like Josiphos, do not make use of potential electron transfers in their applications. Herein, we report a series of compounds where bis(diphenylphosphino)acetylene (dppa) is coordinated to a tungsten (II) centre in the η2-c,c -fashion. Since dppa tends to bind to metals via one of its phosphorous atoms in the end-on-mode, it has to be introduced by stepwise deprotonation and P-functionalization of the corresponding C2H2-complex. The compounds thus produced can subsequently be coordinated to another transition metal, the catalytic properties of which shall be determined in the near future. Figure 1. dppa-tungsten-complex (left) and variations in the oxidation potential depending on the ligand X (right). As shown in Figure 1, even varying the type of anionic co-ligand attached to the metal leads to drastic changes in the oxidation potential (see also[2]). Variations of the type of phosphines used, a possible exchange of the CO-ligand for isonitriles or even a second anionic ligand, as well as the use of molybdenum in place of tungsten leaves manifold possibilities, allowing for the tuning of the potential to the one required for the catalytic task at hand. A. Togni, C. Breutel, A. Schnyder, F. Spindler, H. Landert, A. Tijani, J. Am. Chem. Soc. 1994, 116, [2] N. G. Conelly, C. J. Adams, I. M. Bartlett, S. Carlton, D. J. Harding, O. D. Hayward, A. G. Orpen, E. Patron, C. D. Ray, P. H. Rieger, Dalton Trans. 2007, 1,

56 Novel chelate ligands for stabilization of low-valent group 13 metal centres Johannes Kretsch and Dietmar Stalke* Institute for Inorganic Chemistry Georg-August-University Goettingen Tammannstr Goettingen Nowadays, a lot of new compounds with low-valent group 13 and 14 elements are reported wherein the β-diketiminate ligand (nacnac) is one of the most prominent structural motif. These low-valent main group complexes can be used for catalytic transformations. In our recent work the nacnac is mimicked via bis-heterocyclomethane[2] derivatives (1) (Fig. 1). Figure 1. Synthetic route: i) Deprotonation of the nacnac analog[2] and ii) salt elimination towards a halide complex (3). For the synthesis of a metalla carbene, which has an active metal center, it is necessary to fine tune the structural and electronic properties of the nacnac analog (1). Therefore different organic residues (R) have been introduced to the aryl system and the ligands back bone (R ) as well as variations of the linker atom X (X = O, S). After initial synthesis of the bis-heterocyclomethane derivative (1), a deprotonation step by a strong base like n-butyllithium or potassium hydride is introduced. Subsequently salt elimination is done by adding a metal halide M Z3 (M = In, Ga, Al; Z = Cl, I). The obtained metal halide complex (3) can be reduced by strong reducing agents like potassium graphite and further functionalized. All compounds herein could be charaterized by single crystal X-ray analysis and multinuclear NMR spectroscopy. a) S. Nagendran, H. W. Roesky, Organometallics 2008, 27, b) M. Asay, C. Jones, M.Driess, Chem. Rev. 2011, 111, [2] a) D.-R. Dauer, D. Stalke, Dalton Trans. 2014, 43, b) D-R. Dauer, M. Flügge, R. Herbst-Irmer, D. Stalke, Dalton Trans. 2016, 45,

57 Mes*2NP3Cl2 A novel P3N ring system? Jonas Bresien,a Alexander Hinz,c Axel Schulz,a,b* Tim Suhrbier,a and Alexander Villingera a Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-EinsteinStraße 3a, Rostock, Germany. b c Leibniz-Institut für Katalyse e.v. an der Universität Rostock, Albert-Einstein-Straße 29a, Rostock, Germany. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, Great Britain. jonas.bresien@uni-rostock.de, axel.schulz@uni-rostock.de Ring systems based on group 15 elements (pnictogens, Pn) have been in the focus of chemical research for almost 150 years. Especially, N2P2 cycles of the type [XP(µ-NR)]2 (A, R = C or Si based substituent, X = (pseudo)halogen) have been thoroughly investigated over the past few decades.[2] Just recently, we studied closely related P4 ring systems of the type [XP(µ-PR)]2 (B), which can be regarded as heavy homologues of A.[3] Intriguingly, little is known about four membered cycles containing three phosphorus and one nitrogen atom (NP3).[4] In the light of our recent studies on systems of type B, we are currently investigating ring systems of type C (Scheme 1), a formal blend of structures A and B. Scheme 1. Ring systems of type A, B and C. Starting from Mes*PPN(H)Mes* (1, Mes* = 2,4,6-tri-tert-butylphenyl),[5] it was possible to generate the novel diphosphene Mes*PPN(PCl2)Mes* (2), a formal open-chain isomer of the desired ring system Mes*2NP3Cl2 (3). Ongoing studies reveal that compound 2 can be isomerized to the ring system 3 in polar solvents, and the stability of the latter is currently under investigation with respect to [2+2] cycloreversion reactions. a) H. Köhler, A. Michaelis, Ber. Dtsch. Chem. Ges. 1877, 10, ; b) A. Michaelis, G. Schroeter, Ber. Dtsch. Chem. Ges. 1894, 27, [2] G. He, O. Shynkaruk, M. W. Lui, E. Rivard, Chem. Rev. 2014, 114, [3] J. Bresien, C. Hering, A. Schulz, A. Villinger, Chem. Eur. J. 2014, 20, [4] a) E. Niecke, R. Rüger, B. Krebs, M. Dartmann, Angew. Chem. 1983, 95, ; b) D. Gudat, M. Link, G. Schröder, Magn. Reson. Chem. 1995, 33, [5] E. Niecke, B. Kramer, M. Nieger, Organometallics 1991, 10,

58 Melting temperatures and solubilities of Zn(NO3)2 6H2O nanocrystals confined in mesoporous materials Tobias Grünzel, und Michael Steiger* Fachbereich Chemie, Universität Hamburg The Gibbs energy of nanocrystals increases with decreasing crystal size due to an increasing surface to volume ratio (A/V) resulting in a solubility increase and a melting temperature decrease of small crystals. The additional energy of a small crystal is accounted for by the surface energy cl yielding an expression for the solubility increase of nanocrystals. For the thermodynamic solubility product of small crystals we obtain: lnk = lnk + ( cl Vm/RT) (da/dv) (1) where K and K are the thermodynamic solubility product of the small and an infinitely large crystal, respectively, cl is the surface free energy of the crystal liquid interface, Vm is the molar volume of the solid, R is the gas constant and T is the absolute temperature. The surface to volume ratio is inversely proportional to the crystal size. For a spherical crystal of radius r, da/dv = 2/r. The solubility curve of a hydrated salt, i.e. the relation between composition of the saturated solution and temperature, is a continuous function with a maximum if temperature is the ordinate and composition the abscissa. The maximum of the curve is the melting temperature of the hydrated solid and the composition of the saturated solution (the solubility at the melting temperature) equals the composition of the solid. Therefore, as shown in Fig.1, the melting temperature decrease Tm of a small crystal corresponds to a solubility increase msat. Thus, the solubility increase of small crystals can be determined indirectly by measurement of the melting temperature. In the present study, we have determined the melting temperatures of nanocrystals of zinc nitrate tetrahydrate, Zn(NO3)2 6H2O, confined in mesoporous materials with narrow pore size distributions and different pore diameters (Vycor glass, mesoporous silica). Using a molality based Pitzer model for the calculation of water activity and activity coefficients, the thermodynamic solubility products of the nanocrystals were calculated. Using Eq. (1) and treating cl as an adjustable parameter, the data were used to determine values of the surface free energy of the crystal liquid interface. Fig. 1 Solubility curves of a bulk salt hydrate and of nanocrystals (in mesopores). The melting point decrease Tm corresponds to a solubility increase msat at the melting temperature of the small crystal. M. Steiger, J. Cryst. Growth 2005, 282,

59 Chromium and Titanium Phenoxy-Pyridine-type Complexes for the Polymerisation and Co-polymerisation of Olefins Jia-Pei Du, Inke Siewert* Institute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstr. 4, D Göttingen, Germany Corresponding Author: Since the early discovery of the Ziegler-Natta catalysts there has been an increasing academic and industrial interest to develop polymerisation catalysts with enhanced performances and a better control over the molecular weight distribution and the stereochemistry of the resulting polymers. Further development led to the discovery of a new class of polymerisation catalysts, the so-called FI catalysts. In the last decade several metal complexes with phenoxyimine-type ligands bearing two donor atoms have been established as polymerisation catalysts.[2] Recent results showed, that early transition metal complexes with FI-type ligands bearing a third donor unit catalyse the olefin polymerisation with high yields.[3] Not only polymers resulting from olefin polymerisations are of great use, but also functionalised polyolefins obtained by co-polymerisation of olefins with polar monomers such as methyl methacrylate, acrylates, and vinyl acetate.[4] Developments in this area have led to the design of catalysts with mostly late transition metals as metal centre.[5] However, there are only few examples of titanium-based complexes with tridentate ligand systems which show activity in co-polymerisation.[6] These results prompted us to develop tridentate ligand systems with an N,N,O-donorset bearing a phenoxy- or an anisole-, a pyridinyl- and a imidazolyl-unit. The ligands were utilised to design chromium and titanium complexes and the respective complexes were then investigated upon their activity in olefin polymerisation and co-polymerisation. a) V. C. Gibson, S. K. Spitzmesser, Chem. Rev. 2003, 103, 283.; b) S. D. Ittel, L. K. Johnson, M. Brookhart, Chem. Rev. 2000, 100, [2] a) R. Furuyama, T. Fujita, F, S, Funaki, T. Nobori, T. Nagata, K. Fujiwara, Catal. Surv. Asia 2004, 8, 61.; b) M. Mitani, J. Saito, S. Ishii, Y. Nakayama, H. Makio, N. Matsukawa, N. Matsui, J. Mohri, R. Furuyama, H. Terao, H. Bando, H. Tanaka, T. Fujita, Chem. Rec. 2004, 4, 137. [3] a) E. Kirillov, T. Roisnel, A. Razavi, J.-F. Carpentier, Organometallics 2009, 28, 2401.; b) A. K. Tomov, J. J. Chirinos, D. J. Jones, R. J. Long, V. C. Gibson, J. Am. Chem. Soc. 2005, 127, [4] L. S.Boffa, B. M. Novak, Chem. Rev. 2000, 100, [5] a) L. K. Johnson, S. Mecking, M. Brookhart, J. Am. Chem. Soc. 1996, 118, 267.; b) T. R. Youkin, E. F. Conner, J. I: Henderson, S. K. Friedrich, R. H. Grubbs, Science 2000, 287, 460.; c) V. C. Gibson, A. Tomov, Chem. Commun. 2001, 1964.; d) X.-F. Li, Y.-G. Li, Y.-S. Li, Y.-X. Chen, N.-H. Hu, Organometallics 2005, 24, [6] a) X.-H. Yang, C.-R. Liu, C. Wang, X.-L. Sun, Y.-H. Guo, X.-K. Wang, Z. Xie, Y. Tang, Angew. Chem., Int. Ed. 2009, 48, 8099.; b) M. Gao, C. Wang, X. Sun, C. Qian, Z. Ma, S. Bu, Y. Tang, Z. Xie, Macromol. Rapid Commun. 2007, 28, 1511.; c) M.-L. Gao, X.-L. Sun, Y.-F. Gu, X.-L. Yao, C.-F. Li, J.Y. Bai, C. Wang, Z. Ma, Y. Tang, Z. Xie, S.-Z. Bu, C. Qian, J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 2807.

60 Untersuchung von peri-substituierten Phosphonium-Silicium-AcenaphthenVerbindungen Sebastian Holsten, Emanuel Hupf, Enno Lork, Jens Beckmann* Universität Bremen, Institut für anorganische Chemie und Kristallographie, Loebener Straße, Bremen, Die Verbindung 5-Diphenylphosphinoacenaphthen-6-yl-dimethylsilan (2), wie auch das entsprechende Silanol, wurden im Rahmen der AG Beckmann vollständig charakterisiert und Interaktionen der Substituenten in peri-position untersucht. Durch Oxidation des Phosphors mit Chalkogenen (O, S, Se) verstärkt sich die repulsive Wechselwirkung zwischen Phosphor und Silicium. Ähnliche Wechselwirkung wurden am Phosphonium-Triflat (3) beobachtet. Folgend wird der Syntheseweg und die Kristallstruktur von (3) gezeigt: Schema 1. Syntheseweg des Phosphonium-Triflates. Abbildung 1. Kristallstruktur des Phosphonium-Triflates (3). Hervorzuheben ist der Abstand zwischen dem Phosphoratom und dem Methylkohlenstoffatom, welcher einer P-C-Einfachbindung ähnelt, jedoch kürzer ist als eine typische P-Chalkogen-Doppelbindung. Weitere Forschung bezüglich der Reaktivität des Phosphonium-Ions, sowie der Siliciumfunktion ist hierbei interessant. E. Hupf, E. Lork, S. Mebs, J. Beckmann, Organometallics 2015, 34,

61 Die erste Niob-Clusterverbindung mit gleichzeitig innen-außen verknüpfenden Liganden: [Nb6(OC2H4NH2)6I-A(OC2H4NH2)6I]I3, Synthese und Charakterisierung Daniel Holger Weiß, Arne Pigorsch und Martin Köckerling* Universität Rostock, Institut für Chemie, Albert-Einstein-Straße 3a, Rostock Die einzigen bisher bekannten hexanuklearen Clusterverbindungen mit oktaedrischen Metallatomkernen, die durch intramolekulare Chelatliganden verbrückt werden, sind Re-Clusterverbindungen mit verbrückenden Phosphin-Liganden. Von allen anderen frühen Übergangsmetallen existieren bisher keine M6-Clusterverbindungen (M = Nb, Ta, Zr, Hf) mit Chelatliganden. Die neue Clusterverbindung [Nb6(OC2H4NH2)6I-A(O C2H4NH2)6I]I3 ist somit der erste Vertreter dieser Gattung. Es liegt ein Cluster vom M6X12-Typ vor, in dem sechs innere[2] und gleichzeitig sechs äußere Clusterpositionen von 2-Aminoethanolat-Liganden verbrückend besetzt sind. Sechs weitere 2-Aminoethanolat-Liganden besetzen nicht-verbrückend O-koordiniert die restlichen inneren Clusterpositionen (s. Abb.1). Die Synthese dieses Clusters weist eine weitere Besonderheit auf, eine Transformation eines M6X8-Clsuters zu einem vom M6X12-Typ mit gleichzeitigem Austausch der kompletten Ligandensphäre. Diese Konformationsänderung ist ebenfalls ein völlig neues Konzept in der M6Clusterchemie. Für die Bildung der Titelverbindung lässt sich folgende Reaktionsgleichung formulieren: [Nb6I11] + 12 HOC2H4NH2 + 8 NC5H5 [Nb6(OC2H4NH2)6I-A(O C2H4NH2)6I]I3 + 8 INC5H6 + 2H2 Abb.1. Darstellung der kationischen Clustereinheit (ohne Wasserstoffatome und Anionen) in Kristallen von [Nb6(OC2H4NH2)6I-A (OC2H4NH2)6I]. Ein Chelatligand ist mit grünen Bindungen und ein nichtchaltisierender innerer Ligand mit blauen Bindungen hervorgehoben. Z. Chen, T. Yoshimura, M. Abe, Angew. Chem. Int. Ed. 2001, 40, [2] A. Simon, H. Schnering, H. Schäfer, Z. Anorg. Allg. Chem. 1967, 355,

62 Synthese neuartiger Vanadium(IV/V)Katalysatoren für die enantioselektive Oxidation von prochiralen Sulfiden Lina Fischer, Carola Schulzke* Institut für Biochemie, Universität Greifswald, Felix-Hausdorffstraße 4, Greifswald, Die Bandbreite der bekannten stickstoff- und/oder sauerstoffhaltigen Vanadiumkatalysatoren soll um die schwefelhaltigen Dithiolene erweitert werden. Die Dithioleneinheit ist aus den aktiven Zentren der Molybdän- und Wolfram-Oxidoreduktasen bekannt. Dithiolene besitzen einen sogenannten non-innocent - Charakter, d.h. sie nehmen Einfluss auf die Oxidationszahl des Metallzentrums und können so Oxidations- bzw. Reduktionsreaktionen beeinfluss. Die Verbindung dieses Ligandentyps mit Vanadium könnte zu vielversprechenden Katalysatoren für Oxidationsreaktionen führen. Bis- und Tris-Dithiolen-Vanadium-Komplexe sind in der Literatur beschrieben und gelten als thermodynamisch stabil und somit katalytisch inaktiv. Diese werden von Vanadium bevorzugt gebildet, da es stark zur Bildung homoleptischer Komplexe neigt. Auch in diesem Projekt sind verschiedene Bis-Dithiolen-Vanadium-Komplexe entstanden. Beispielhaft ist ein Komplex einer ungewöhnlichen Koordination in Abbildung 1. dargestellt. Um das Vanadiumzentrum in eine heteroleptische Konformation zu zwingen und somit Mono-Dithiolen-Vanadium-Komplexe zu erhalten, wird an der Synthese von sterisch anspruchsvollen Liganden und Dithiolenen gearbeitet. Später soll das Ligandensystem um chirale Liganden erweitert werden. O N N V N N O N S N S V S N S 2 CH3CN N Abbildung 1. Molekülstruktur und chemische Formel von [V2O(µ-O)(Bipyridin)2 (Maleonitrildithiolen)2] 2CH3CN. Mono-Dithiolen-Vanadium-Komplexe sollen dann schließlich in der enantioselektiven Oxidation von prochiralen Sulfiden zur Synthese von chiralen Sulfoxiden getestet werden, da chirale Sulfoxide wichtige Bausteine in der Synthese von chiralen Feinchemikalien und Pharmazeutika darstellen.

63 Ligand centered radical reactivity of a Ni(III) PNP Pincer Complex Felix Schneck, Markus Finger und Sven Schneider* Georg-August Universität Göttingen, Tammannstraße 4, Göttingen The ability of ligands to act as proton or electron reservoir is summarized as cooperative or non-innocent behaviour respectively and has gained considerable attention in the past few decades. Especially the multi-electron redox activation of small molecules by base-metals has made great progress due to use of non-innocent ligands, since 3d metals are more prone to 1e- redox-processes than their higher homologues.[2] Herein we describe the synthesis of the new [(PNP)NiBr] (PNP = N(CHCHPtBu2)2) pincer complex 1 bearing bulky tbu substituents and a divinylamido backbone (Figure 1). 1-Electron oxidation yields compound 2 with an oxidized PNP ligand according to DFT and EPR analysis.[3] As a result, radical reactivity with organic substrates is observed to yield Ni(II) complex 3 by formal hydrogen atom abstraction. Experimental determination of the C-H bond dissociation enthalpy of 3 was carried out according to a thermodynamic cycle by separation of the protonation and oxidation step.[4] Figure 1. Reactivity of new compounds 1, 2 and 3. Literature: (a) C.K. Jørgensen, Coord. Chem. Rev. 1966, 1, (b) W. Kaim, Inorg. Chem. 2011, 50, (c) H. Grützmacher, Angew. Chem. Int. Ed. 2008, 47, [2] (a) P.J. Chirik, K. Wieghardt, Science 2010, 327, (c) C. Gunanathan, D. Milstein, Acc. Chem. Res. 2011, 44(8), [3] D. Adhikari, S. Mossin, F. Basuli, J.C. Huffmann, R.K. Szilagyi, K. Meyer, D.J. Miniola, J. Am. Chem. Soc. 2008, 130, [4] (a) F.G. Bordwell, J.-P. Cheng, J.A. Harrelson, Jr., J. Am. Chem. Soc. 1988, 110, (b) J.J. Warren, T.A. Tronic, J.M. Mayer, Chem. Rev. 2010, 110,

64 Iron catalyzed dehydropolymerization of methylamine borane Felix Anke, Marcus Klahn, Torsten Beweries* Leibniz-Institut für Katalyse e.v. an der Universität Rostock, Albert-Einstein-Str. 29a, Rostock, Catalytic routes for the formation of bonds between main group elements are very important for targeted construction of new molecules and materials. In contrast to the formation of C-C bonds or C-X bonds, main group bond-forming reactions lag behind. For instance catalytic dehydropolymerization reactions of amine borane adducts (RNH2 BH3, R = H, Me) provide a clean, atom efficient route to synthesize polyamineboranes, involving the loss of hydrogen. These polymeric BN materials are isoelectronic to technologically versatile polyolefins and are discussed as high performance polymers, as precursor to BN-based ceramics and singlelayer hexagonal BN thin films (white graphene). These dehydrocoupling reactions offer significant advantages over previous classical methods such as reductive coupling, high temperature condensation or salt metathesis.[2] In 2010 the Manners group demonstrated that MeNH2 BH3 can be dehydrocoupled by transition metal complexes to afford a linear polyamineborane.[3] In recent years our group focused on the catalytic dehydrogenation of dimethylamine borane to dimeric compounds by group 4 metallocene complexes.[4] Scheme 1. Iron complex catalyzed dehydropolymerization of methylamine borane. Herein we describe the use of a pincer PNHP iron complex bearing a η1-hbh3 ligand as a highly active catalyst for dehydrocoupling of methylamine borane at room temperature to give mainly linear high molecular weight polyamineborane. The resulting polymeric compound was fully characterized by NMR, IR, ESI-MS and GPC. H. C. Johnson, E. M. Leitao, G. R. Whittell, I. Manners, G. C. Lloyd-Jones, A. S. Weller, J. Am. Chem. Soc. 2014, 136, [2] R. L. Melen, Chem. Soc. Rev. 2016, 45, [3] A. Staubitz, M. E. Sloan, A. P. Robertson, A. Friedrich, S. Schneider, P. J. Gates, J. S. a. d. Guenne, I. Manners, J. Am. Chem. Soc. 2010, 132, [4] a) T. Beweries, S. Hansen, M. Kessler, M. Klahn, Uwe Rosenthal, Dalton Trans. 2011, 40, ; b) M. Klahn, D. Hollmann, A. Spannenberg, A. Brückner, T. Beweries, Dalton Trans. 2015, 44,

65 Rhenium-compound Essential for oxidative addition/reductive elimination Sequence Dithienylethene (DTE) 1 Reduction of 1 with potassium leads to a ch Photo-Switchable Electromeric Complexes Bearing Dithienylethene Ligand Motifs shift of the thienyl-protons H in H-nmr fro ppm to 5.94 ppm. This might alread Controllable Redox Non-Innocence Induced by External Stimuli in a V(IV)6.26 Complex towards a closed-ring structure, but further 1 a Dithienylethenes are interesting molecular Molecular Recognition Studies switches, which upon irradiation Dirk%Schlüter,%Sarah%Matz,%%Enno%Lork%and%Matthias%Vogt*% can toggle Suitable electron-deficient substance TCNQ between an open ring and a closed ring structure required to proof this presumption. Vanadium-compound University%of%Bremen,%Institute%of%Inorganic%Chemistry%and%Crystallography,%Leobener%Str.,%28359% Electromers 2 Bremen,%Germany%%dirkschl@gmx.de% 2 1.2" 1" 0.8" Absorp'on) Electromers are entities with substantial different electronic structures and only slight Crystal Structures with ligands, which can exist in differences in their geometrical structures.1,2 Metal complexes different oxidation states (non-innocent), exhibit electromerism oflengths the [Å] general form Mx L(II)y? Bond x+n y-n 2.121(1) in major changes in M L. Only marginal geometric changes in the ligand Re-N1 can result 3 C1-N (5) spin-density distribution. Inspired by these findings, we are developing persistent-radical Upon irradiation with UV-light a solution of 2 C1-C (5) turned pink. Currently we are aiming f complexes, in which subtle geometrical changes in the ligand sphere cause significant C2-N (0) characterization of this species. Re-N (1) alteration of the radical nature. Such systems cannot only find applications in information storage, but also in reversible substrate binding, or 1contrast agents for medical applications. Pink" 0.6" Blue" 0.4" 0.2" S2 0" 250" 350" 450" 550" 650" 750" 850" 950" Wavelength)[nm]) S1 C1 C2 N2 N1 Electromers are entities with substantial different electronic structures and (usually) only slight 2,3 differences in their geometrical structures. O O Unlike resonance structures, each of the electromeric species relate to a distinct stable S S ground state Nwith Cl its local minimum on the 1 potential energy N 1/2 N Vhyper-surface. THF, reflux, 24h Transition metal ligands, which N complexes with Cl -TMEDA can exist in different oxidation states (non48% innocent), exhibit electromerism of the general 2x-n x y y+n form M L M L. Only marginal geometric changes in the ligand scaffold can result in major changes in spindensity distribution within the molecules.4 A C Bond lengths [Å] V-O (3) C1-O (0) C1-C2 S1.364(4) O N C2-O (9) S N V O V-O (8) O O V-O (0) C3-O (5) C3-C4 S (4) S C4-O (5) V-O (7) Re References B S2 S1 O1 C3 O C1 V C4 C2 S3 O3 O4 S4 C. K. Jorgensen, Coord. Chem. Rev. 1966, 1, B. Müller, T. Bally, F. Gerson, A. de Meijere, M. v. Seeb Am. Chem. Soc. 2003, 125, T. Bally, Nat. Chem. 2010, 2, F. F. Puschmann, J. Harmer, D. Stein, H. Rüegger, B. d H. Grützmacher, Angew. Chem. 2009, 122, L. I. Belen'kii, V. Z. Shirinyan, G. P. Gromova, A. V. Kolot A. Strelenko, S. N. Tandura, A. N. Shumskii, M. M. Kray Chem. Het. Comp. 2003, 39, J. T. Price, P. J. Ragogna, Chem. Eur. J. 2013, 19, P. B. Hitchcock, D. L. Hughes, G. J. Leigh, J. R. Sanders, de Souza, J. Chem. Soc., Dalton Trans., 1999, R. J. Bouma, J. H. Teuben, W. R. Beukema, R. L. Bansem C. Huffman, K. G. Caulton, Inorg. Chem. 1984, 23, J. J. H. Edema, W. Stauthamer, F. van Bolhuis, S. Gamba W. J. J. Smeets, A. L. Speks, Inorg. Chem. 1990, M. Farahbakhsh, H. Schmidt, D. Rehder, Chem. Commun UV light open D UV7C" 1.2" E 3 closed F 3 Absorp'on1 1" 0.8" " Pink" Blue" 0.4" 0.2"! 0" 250" 350" 450" 550" 650" 750" 850" 950" 1050" Wavelength1[nm]1 We report on a vanadium(iv) compound (3) bearing a 1,2-di(thiophen-3-yl)ethene-1,2diolate (diothio) ligand, (A, synthesis and B, crystal structure). The cyclic-voltammogram of the diothio ligand shows a reversible- and quasi-reversible redox-wave indicating a stepwise two-electron redox process, F. The EPR spectrum of 3 in solution suggest a V(IV) metallo radical, E. DFT computations also suggest the spin-density mainly centered on V. However, there is significant spin-density distributed within the O C=C O ligand scaffold in 3. The DFT optimized structure of the closed form 3 shows a significant reduction of spin-density in the O C C O unit within the cyclized dithio ligand, C. Complex 3 serves as a prototype to illuminate the concept of switchable electromeric complexes via utilization of non-innocent ligands carrying bistable photoswitchable units. A drastic color change from blue to red can be observed, when a solution of compound 3 in toluene or THF is irradiated with UVC light, D. Our ongoing investigations aim for the structural characterization of the formed species. (1)Müller, B.; Bally, T.; Gerson, F.; de Meijere, A.; Seebach, von, M. J. Am. Chem. Soc. 2003, 125, (2) Bally, T. Nat Chem 2010, 2, 165. (3) Puschmann, F. F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin, B.; Grützmacher, H. Angew. Chem. 2009, 122, 395.

66 Artaios a transport code for post-processing quantum chemical electronic structure calculations M. Deffner1, L. Gross1, T. Steenbock1, B. A. Voigt1, C. Herrmann*1 and G. C. Solomon2 1 Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, Hamburg, Germany 2 Nano-Science Center, University of Copenhagen, DK-2100 Copenhagen, Denmark michael.deffner@chemie.uni-hamburg.de Driven by the idea of using molecules as electronic building blocks, the understanding of electron transport in molecular junctions is an important field of research. The state-ofthe-art theoretical framework to investigate electron transport in the coherent regime is the Landauer Imry Bu ttiker approach. We present our post-processing program Artaios[2], which is based on the Landauer approach in combination with the Green s function method[3]. Several quantum chemical electronic structure codes can be interfaced, or alternatively simple Hu ckel-type Hamiltonians can be post-processed. The program is capable of decomposing the transmission into local contributions (see Figure 1). The subsystem molecular orbitals can be obtained by solving the subsystems secular equations. Additionally, the program offers the possibility of calculating local spins by the Mayer local spin analysis scheme and Heisenberg exchange-spin coupling constants with a Green s function approach[4]. Figure 1: Local transmissions through a meta-substituted phenyl ring at energies of 6.02 ev (left) and ev (right). M Bttiker et al., Phys. Rev. B 31, 6207 (1985). [2] C. Herrmann et al., J. Chem. Phys. 132, (2010). [3] Y. Xue et al., Chem. Phys. 281, 151 (2002). [4] T. Steenbock et al., J. Chem Theory Comput. 11 (12) (2015).

67 Introducing Thallium in Polyoxometalate Chemistry Wassim W. Ayass and Ulrich Kortz* Jacobs University, Department of Life Sciences and Chemistry, P.O. Box , Bremen, Germany. The aqueous solution chemistry of Tl3+ is dominated by a high tendency for hydrolysis, resulting in the formation of Tl3+-hydroxo complexes. Contrary to the lighter metal ions of group 13, Tl3+ does not form polynuclear hydroxo-complexes,1 and compounds with more than one Tl atom are known mainly in organo-thallium chemistry.2 Tl-containing compounds are widely used in electrical, medical, and even glass manufacturing industries.3 The area of Tl-containing POMs is barely investigated. Some thallium salts of di-, para- and metatungstates have been prepared by conventional methods.4 In 1953, Magneli5 first described the structure of hexagonal tungsten bronze AxWO3, and later and Shivahare4 (1964) and Bierstedt6 (1965) isolated Tl0.3WO3 and Tl2W4O13, respectively. These compounds are extended tungsten oxides and hence not classified as POMs. To date no structurally characterized discrete Tl-containing polyanion has been reported. We were inspired by the above work, and thus decided to attempt incorporating thallium in a POM cluster. Herein we report the synthesis and structure of a thallium(iii)-containing tungstosilicate. We also used Tl NMR and ESI-MS to study the solution stability of this compound. C. F., Jr. Baes and R. E. Mesmer, The Hydrolysis of Cations, Wiley-Intersience, [2] A. R. Fox, R. J. Wright, E. Rivard and P. P. Power, Angew. Chem. Int. Ed. 2005, 44, [3] Toxicological Review of Thallium Compounds, U.S. Environmental Protection Agency, [4] G. C. Shivahare, Naturwissenschaften, 1964, 406. [5] A. Magneli, Acta. Chem. Scand., 1953, 7, [6] P. E. Bierstedt, T. A. Bither and F. J. Darnell, Solid State Comm. 1966, 4,

68 Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Achiral Dipyrrinato Ligand Julius F. Kögel,a,b Shinpei Kusaka,a Ryota Sakamoto a,* and Hiroshi Nishiharaa,* a b Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo , Japan. FB Biologie/Chemie, Universität Bremen, Leobener Str. im NW2, Bremen, Germany. sakamoto@chem.s.u-tokyo.ac.jp, nisihara@chem.s.u-tokyo.ac.jp. The directed frontier orbital engineering in heteroleptic dipyrrinato complexes by the systematic choice of the ligands can result in coordination compounds with extremely high fluorescence quantum yields. Herein we present the synthesis of heteroleptic zinc(ii) complexes bearing achiral dipyrrinato and chiral bis(oxazoline) ligands. They show bright fluorescence and high quantum efficiencies of up to This originates from the π-π* photoexcited state localized exclusively on the dipyrrinato ligand. Furthermore, the reported compounds exhibit chiroptical properties and the luminescence is circularly polarized in spite of the achirality of the dipyrrinato ligand: Single-crystal X-ray structure analysis reveals the intramolecular π-π interactions between the chiral bis(oxazoline) ligand and the dipyrrinato ligand, inducing the chiroptical property to the latter. Besides their optical and structural characteristics, the obtained compounds were investigated with respect to their redox behaviour and DFT calculations shed light on the complexes frontier orbitals.[2] Scheme 1. Left: heteroleptic zinc(ii) complexes bearing a dipyrrinato and a bis(oxazoline) ligand; middle: molecular structure of complex (R,R)-1 showing the intramolecular π-π stacking between the two ligands; right: complex (R,R)-1 under irradiation with UV light (365 nm) in CH2Cl2 and toluene. a) S. Kusaka, R. Sakamoto, Y. Kitagawa, M. Okumura, H. Nishihara, Chem. Asian J. 2012, 7, ; b) S. Kusaka, R. Sakamoto, H. Nishihara, Inorg. Chem. 2014, 53, ; c) M. Tsuchiya, R. Sakamoto, S. Kusaka, Y. Kitagawa, M. Okumura, H. Nishihara, Chem. Commun. 2014, 50, [2] a) J. F. Kögel, S. Kusaka, R. Sakamoto, T. Iwashima, R. Toyoda, M. Tsuchiya, R. Matsuoka, T. Takamasa, J. Yuasa, Y. Kitagawa, T. Kawai, H. Nishihara, Angew. Chem. 2016, 128, ; Angew. Chem. Int. Ed. 2016, 55, ; b) R. Sakamoto, T. Iwashima, J. F. Kögel, S. Kusaka, M. Tsuchiya, Y. Kitagawa, H. Nishihara, J. Am. Chem. Soc. 2016, 138,

69 Donor- und Akzeptor-funktionalisierte 2,2'-Bipyridin- und 2-Phenylpyridin-komplexe als Chromophore für die nichtlineare Optik Marie Christin Wolff, Sebastian Triller und Jürgen Heck Insitut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-LutherKing-Platz 6, Hamburg Auf der Suche nach Materialien, die bei Bestrahlung mit Laserlicht möglichst starke nichtlinear optische Effekte, wie z.b. Frequenzverdopplung (SHG), Pockels Effekt, Kerr Effekt zeigen, gelangten dipolare push and pull Chromophore in den Mittelpunkt des Interesses. Derartige Chromophore sollten, nach einer von Ratner et. al. präsentierten Studie, verstärkte NLO Aktivität aufweisen, wenn sie unter Einwirkung von Druck in enge räumliche Nachbarschaft zueinander gebracht werden[2]. [Druck] β r D D A A A D A M1 D A A A N N D D M2 D r A D A D D N A Abbildung 1. Die mögliche Verstärkung NLO - Aktivität (β) durch Anordung von push and pull Chromophoren in enger räumlichen Nachbarschaft zueinander durch Druck[2] oder durch Koordination bzw. zusätzlich Einbau in eine dendritische Struktur. M1 = Ru, Ni, Zn; M2 = Rh, Ir. In der Arbeitsgruppe Heck wird versucht, eine Anordnung in enger räumlicher Nachbarschaft anstatt durch Druck durch Koordination an ein Metallzentrum zu realisieren, wobei als Chromophore Donor- und Akzeptor-funktionalisierte Derivate des 2,2-Bipyridins, sowie des 2-Phenylpyridins eingesetzt werden (Abbildung 1). Eine besondere Schwierigkeit ist es hierbei, die parallele Anordnung Chromophore zueinander sicherzustellen. Dies soll im Falle der Bipyridinkomplexe durch Einbau in eine dendritische Struktur [3], im Falle der tris-cyclometallierten Verbindung durch die thermodynamisch bevorzugte fac-isomerie[4] erreicht werden. Die dendritischen Bipyridinkomplexe konnten inzwischen nicht nur mit Ruthenium, sondern auch mit Nickel und Zink als Zentralmetall synthetisiert werden. Die Cyclometallierung von Donor-/ Akzeptor- substituierten Phenylpyridinen, erwies sich zunächst als nicht praktikabel, allerdings wurde durch das Auffinden einer neuen Cyclometallierungsmethode, die auch bei Raumtemperatur funktioniert anstatt der ansonsten üblichen 230 C [4] auch hier ein entscheidender Fortschritt erzielt und cyclometallierte Phenylpyridine mit Donor-/ Akzeptor-Substitution erstmals vollständig charakterisiert. J. L. Oudar, D. S. Chemla, J. Chem. Phys., 1977, 66, [2] S. Di Bella, M. A. Ratner, T. J. Marks, J. Am. Chem. Soc., 1992, 114, [3] M. Büchert, T. Steenbock, C. Lukaschek, M. C. Wolff, C. Herrmann, J. Heck, Chem. Eur. J. 2014, 20, [4] K. Ono, M. Joho, K. Saito, M. Tomura, Y. Matsushita, S. Naka, H. Okada, H. Onnagawa, Eur. J. Inorg. Chem, 2006, 2006,

70 Phosphorstabilisierte Boreniumionen Sinas Furan, Enno Lork und Jens Beckmann* Institut für Anorganische Chemie, Universität Bremen, Leobener Straße, Bremen, Deutschland, Die peri-substitution hat sich als ein leistungsfähiges Werkzeug zur Untersuchung von ungewöhnlichen Bindungssituationen erwiesen. Die Verwendung eines AcenaphthenGrundgerüsts zwingt die peri-substituierten Atome aufgrund der geringen Konformationsflexibilität des Acenaphthens in Wechselwirkung zu treten. Schema 1. Synthese eines phosphorstabilisierten Boreniumions. Vor allem eignen sich peri-substituierte Diphenylphosphinoacenaphthene, um attraktive intramolekulare P B Wechselwirkungen auszubilden. So kann durch das AcenaphthenGerüst sowie die Lewis-Basizität des Phosphors das äußerst reaktive Boreniumion stabilisiert werden. Boreniumionen dienen aufgrund ihres kationisches Charakters als wertvolle BoranAnaloga und somit als sehr gute Elektrophile.[2] Unser Ziel ist daher die Synthese phosphorstabilisierter Boreniumionen über verschiedene Reaktionswege. J. Beckmann, T. G. Do, S. Grabowsky, E. Hupf, E. Lork, S. Mebs, Z. Anorg. All. Chem. 2013, 639, [2] M. Devillard, R. Brousses, K. Miqueu, Gouhadir, D. Bourissou, Angew. Chem. Int. Ed. 2015, 54,

71 Towards precise and accurate determination of hydrogen atom positions with X-ray diffraction data utilizing hydrogen maleate salts Lorraine A. Malaspina,a Magdalena Woińska,b Regine Herbst-Irmer,c Simon Grabowskya* a Institute for Inorganic Chemistry and Crystallography, University of Bremen, Leobener Str. NW2, Bremen, Germany, simon.grabowsky@uni-bremen.de b c Faculty of Chemistry, University of Warsaw, Pasteura 1, Warsaw, Poland Institute of Inorganic Chemistry, University of Göttingen, Tammannstr. 4, D Göttingen, Germany Hydrogen maleate salts offer the unique opportunity to follow a pseudo-reaction pathway of a proton transfer not only in theoretical simulations but also experimentally because the hydrogen position in the strong and short intramolecular O-H-O hydrogen bond is highly flexible dependent on the cation. There are numerous crystal structures of hydrogen maleate salts in the literature, sowing that the O-H distances vary from 0.88Å and 1.37Å[2] in highly asymmetric hydrogen bonds to 1.22Å[3] in symmetric hydrogen bonds with a large variety of intermediate distances. This means that snapshots along a pseudo-reaction pathway can be measured and with the symmetric hydrogen bonds, even a model for a possible transition state is accessible. Therefore, it is crucial to obtain the precise and accurate position and displacement parameters of the hydrogen atoms, which can only be achieved using neutron-diffraction techniques or new quantum crystallographic techniques based on X-ray data (such as HAR). This capability will be shown using synchrotron data sets of the compounds 4-aminopyridinium, 8-hydroxyquinolinium, barium, calcium, potassium, lithium, magnesium, sodium and L-phenylalaninium[4] hydrogen maleates. It is common to all structures that intermolecular hydrogen bonds are responsible for the packing directed along the molecular plane. These intermolecular interactions together with the varying distance O1...O2 seems to govern the position of the H-atom in the intramolecular hydrogen bond. All structures can be sorted into three groups when considering the position of the H1 atom, one where the position is highly symmetric, one intermediate position and one highly non-symmetric position. Hirshfeld surfaces analyses and fingerprint plots[5] show that O-H bonds are responsible for over 41% of all interactions between the cation and anion, in particular O2...H-D bonds, which represent over 13% of these interactions for all the compounds. A geometrical correlation using the known distances from the non-hydrogen atoms was found to accurately predict the position of the hydrogen atom H1 in question when compared to results from neutron diffraction. F. Vanhouteghem, A. T. H. Lenstra, and P. Schweiss, Acta Cryst. B 1987, 43, [2] G. Olovsson, I. Olovsson, and M. S. Lehmann, Acta Cryst. C 1984, 40, [3] C. C. Wilson, L. H. Thomas, and C. A. Morrison, Chem. Phys. Let. 2003, 381, [4] M. Woińska, D. Jayatilaka, M. A. Spackman, A. J. Edwards, P. M. Dominiak, K. Woźniak, S. Grabowsky, Acta Cryst. A 2014, 70, [5] M. A. Spackman, J. J. McKinnon, CrystEngComm 2002, 66,

72 Development of Ni and Co catalysts for the (co-)polymerization of olefins and polar monomers and hydrofunctionalization of olefins Andreea Enachi, Matthias Freytag, Peter G. Jones, Marc Walter* TU Braunschweig, Institute for Inorganic and Analytical Chemistry, Hagenring 30, Braunschweig, Germany Transition metal alkyl complexes are among the most reactive species in organometallic chemistry, therefore preparing and isolating them can be a challenge. However, we were able to synthesize dialkyl metal complexes in a good yield using [(tmeda)m(acac)2] (M=Ni, Co) as a M2+ source and [(tmeda)mgr2] (R= CH2SiMe3, CH2CMe2Ph) as the alkyl transfer reagent. Furthermore, the tmeda ligand can be readily displaced by tunable bidentate phosphines and N-heterocyclic carbenes (NHCs) which are good sigma donors and spectator ligands and confer good stability to transition metal complexes. The lower oxophilicity and presumed greater functional-group tolerance of late transition metals relative to early metals make them promising targets for the development of catalysts suitable for the preparation of ethylene and polar vinyl monomer copolymers which are currently industrially prepared by radical polymerization.[2] This and further applications in the hydrofunctionalization of olefins and functionalized olefins will be reported. Schema 1. Preparation of N-heterocyclic carbene Ni2+ and Co2+ dialkyl compounds. 1 [2] 2 Zhu, D.; Janssen, F.F.B.J.; Budzelaar, P.H.M. Organometallics 2010, 29, a) Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc. 1996, 118, 267; b) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120, 888.

73 Flüssige Eisen-Schwefel-Cluster Neue Elektrolyte für Redox-Flow-Batterien Christian Modrzynski, Peter Burger* Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, D Hamburg I [µa] Potential [mv] vs. SHE Schema 1. Imidazolium Eisen-Schwefel-Cluster: Struktur, Eigenschaften und CV. Fluktuierende Energiequellen (PV, Wind) sind die tragenden Säulen der Energiewende. Dies erfordert effiziente elektrische Speicher, um die Versorgungsicherheit zu gewährleisten. Redox-Flow-Batterien sind hierfür potentielle Kandidaten, die bisher jedoch eine sehr geringe Energiedichte aufweisen. Für neue anodische Elektrolyte wurden ionischen Flüssigkeiten mit einer redoxaktiven Komponente dargestellt. Diese basiert auf den aus der Natur bekannten Eisen-SchwefelCluster.[2] Die Synthesen und elektrochemischen Eigenschaften dieser neuen flüssigen Elektrolyte werden vorgestellt und hinsichtlich ihres Einsatzes in Redox-Flow-Batterien diskutiert. F. Rahman, M. Skyllas Kazacos. J Power Sources 2009, 189, [2] P. Venkateswara Rao, R. H. Holm, Chem. Rev., 2004, 2, 527.

74 Activation and Coupling Studies of Pyridin-Diimin-Complexes with Dioxygen Max Völker and Peter Burger* University of Hamburg, Martin-Luther-King-Platz 6, Hamburg Catalytic (di-) hydroxylation of organyls by activating and coupling molecular oxygen is a scientific area under investigation. Neutral PDI-complexes has shown the ability to bind oxygen to form peroxo-complexes. Based on elaborate theoretical studies a cationic PDIcomplex should activate dioxygen and form a trigonal bipyramidal bis-oxo-pdi-complex (fig. 1). Further reaction with dihydrogen or olefins to dihydroxylated species are thermodynamic favored. Synthesis and analysis of neutral peroxo-pdi-complex as reference substance will be reported. Further latest results of investigation on cationic species will be presented. Figure 1. Theoretical equilibrium between in plane peroxo-pdi-complex (left), out-of plane peroxo-pdi-complex (middle) and trigonal bipyramidal bis-oxo-pdi-complex (right).

75 Temperature-dependent investigation of Na8(MO4) [AlSiO4]6 (M = Cr, Mo, W) cancrinites. Hilke Petersen, Lars Robben and Thorsten M. Gesing Institut für anorganische Chemie und Kristallographie, FB2, Leobener Str./NW2, Universität Bremen, Bremen Cancrinite (CAN) to nosean (NOS) phase transformation were first described in 2006 by Jordan et al. for the chromate containing compound. Investigating the thermal behavior and structural developments of these phases, a comparative study was possible with two newly synthesized compounds. Replacing the two fold negative charged CrO42- anion by MoO42- or WO42- was successful during the cancrinite synthesis. Both cancrinites show the similar phase transformation and the latter one is compared here with the chromate behavior. The compounds were synthesized hydrothermally at 473 K (Cr) and 503 K (W) using NaAlO2, Na2SiO3, NaOH and Na2MO4 in a molar ratio of 1:1:16:3 (X = Cr) and 1:1:4:3 (X = Mo, W), respectively. The compounds were investigated by ex-situ annealing experiments as well as in-situ temperature-dependent (TD) X-ray powder diffraction evaluated by Rietveld refinements. The cell volume of the chromate CAN shows a strong increase between 300 K and 400 K while the tungstate CAN increases only very slightly. Around 400 K a similar cell volume for both compounds could be observed and at higher temperatures both expansion curves show a comparable behavior. The compounds show a maximum thermal expansion coefficient (TEC) at 980 K and 915 K for chromate and tungsten, respectively. Upon decrease of the TEC the crystallite sizes start to decrease along with a jump in the strain and first reflections of the NOS type structure could be observed. The ex situ annealing experiments of the three compounds with varying temperatures and annealing times imply a first order reaction for the formation of the NOS type phases. The reaction rate k for the three different compounds are all in the order of 10-6 Lmol-1s-1. Schema 1: TD volume change (left) and the TEC (right) of the chromate and tungsted CAN. E. Jordan, R.G. Bell, D. Wilmer, H. Koller, Anion-promoted cation motion and conduction in zeolites., J. Am. Chem. Soc. 128 (2006) doi: /ja

76 PNP Fe complexes as selective and highly active catalysts for dehydrogenation of hydrazine borane Delong Han, Torsten Beweries* Leibniz-Institut für Katalyse e.v. an der Universität Rostock, Albert-Einstein-Str. 29a, Rostock, When produced using economically friendly techniques, due to its high energy capacity, hydrogen is believed as an alternative to traditional fossil fuels. While, taking the properties of hydrogen under consideration, ideal hydrogen store materials are necessary for the realization of a so-called hydrogen economy. Hydrazine borane (HB), as a promising hydrogen storage material, has outstanding advantages in terms of high gravimetric hydrogen capacity (15.4 %), facile synthesis and long term stability.[2] Thus, it is worth developing efficient methods to release hydrogen from it. Various means have been explored to release hydrogen from HB[3], but only a handful of organometallic complexes were applied as dehydrogenation catalysts.[4] By now, our group has accomplished the study on dehydrogenating HB using Brookhart s Ir hydride complex and its derivatives[5] as catalysts. Experimental data reveals is that the series of [(R2POCOP)IrHX] (R = COOMe, H, t-bu; X=H, Cl) are selective and efficient catalysts for dehydrogenation of HB. After that, Fe based catalysts with PNP pincer ligands were chosen since iron is an earth-abundant non-noble metal and molecularly defined iron pincer catalysts were reported as active catalyst for dehydrogenating amine borane efficiently.[6] We give insights into a series of Fe complexes with the same ligand backbone for catalytic HB dehydrogenation. Scheme 1. Fe complex catalyzed dehydrogenation of hydrazine borane. T. B. Marder, Angew. Chem. Int. Ed. 2007, 46, [2] R. Moury, J. Hannauer, P. Miele, E. Petit, U. B. Demirci, Phys. Chem. Chem. Phys. 2012, 14, [3] Selected examples: (a) J. Hannauer, O. Akdim, P. Miele, J. Herrman, U. B. Demirci, Q. Xu, Energy Environ. Sci. 2011, 4, (b) R. Moury, T. Ichikawa, J. F. Petit, U. B. Demirci, Int. J. Hydrogen Energy 2015, 40, (c) W. B. Aziza, Q. Xu, P. Miele, J. F. Petit, P. Miele, U. B. Demirci, Int. J. Hydrogen Energy 2014, 39, [4] J. Thomas, M. Klahn, A. Spannenberg, T. Beweries, Dalton Trans. 2013, 42, [5] D. Han, M. Joksch, M. Klahn, A. Spannenberg, H.-J. Drexler, W. Baumann, H. Jiao, R. Knitsch, H. Eckert, T. Beweries, submitted. [6] A. Glüer, F. Moritz, V. R. Celinski, M. C. Holthausen, S. Schneider, ACS Catal. 2015, 5, 7214.

77 Synthese und Charakterisierung neuer Molybdän-Distickstoff-Komplexe mit linearen tridentaten PEP-Liganden (E = P, N) K. Grund, S. Hinrichsen, A.-C. Schnoor, B. Flöser, A. Schlimm, C. Näther, J. Krahmer and F. Tuczek* Institut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Str. 2, Kiel, Deutschland, kgrund@ac.uni-kiel.de Die Umwandlung von molekularem Stickstoff in bioverfügbare Verbindungen ist eine der wichtigsten Reaktionen der Natur. Im Rahmen der synthetischen Stickstoff-Fixierung liegt ein Forschungsschwerpunkt unserer Arbeitsgruppe in der Entwicklung von MolybdänDistickstoff-Komplexen mit Liganden, die im Gegensatz zu klassischen Chatt-Systemen die trans-position zum N2-Liganden absättigen. Dies beinhaltet z.b. die Verwendung von linearen tridentaten PEP-Liganden (E = P, N) in Kombination mit bidentaten Coliganden. In Anlehnung an den von GEORGE et al. synthetisierten Komplex [Mo(N2)(dpepp)(dmpm)] (dpepp = PhP(CH2CH2PPh2)2, dmpm = (CH3)2PCH2P(CH3)2) haben wir eine Reihe ähnlicher Komplexe mit facial koordinierten tridentaten Liganden hergestellt und spektroskopisch untersucht (Schema. 1).[2, 3] Schema 1. Übersicht der synthetisierten und untersuchten Komplexe, ausgehend von [Mo(N2)(dpepp)(dmpm)]. Von besonderem Interesse war dabei für uns, wie sich eine Verlängerung der C2-Kette des dpepp-liganden durch eine weitere Methylengruppe auf die Stabilität und Aktivierung des N2-Komplexes auswirkt. Darüber hinaus wurden der Einfluss des trans-ständigen tertiären Phenylphosphin-Donors gegenüber einem sekundären Phosphin sowie der Austausch des zentralen P-Donoratoms durch einen N-Donor auf die genannten Eigenschaften untersucht.[3] J. Chatt, A. J. Pearman and R. L. Richards, Nature, 1975, 253, [2] T. A. George and R. C. Tisdale, Inorg. Chem., 1988, 27, [3] S. Hinrichsen, A.-C. Schnoor, K. Grund, B. Flöser, A. Schlimm C. Näther, J. Krahmer and F. Tuczek, Dalton Trans., 2016, eingereicht z. Veröffentlichung

78 Das Hamburger JungChemikerForum Wir freuen uns, Euch beim Norddeutschen-Doktoranden-Kolloquium begrüßen zu dürfen! Das JungChemikerForum der Gesellschaft Deutscher Chemiker (GDCh) engagiert sich international, deutschlandweit und auf regionaler Ebene. Unser Ziel ist der Austausch mit unter Chemikern und das Vermitteln von Potential und Notwendigkeit der Chemie in unserer Gesellschaft. Einige unserer Projekte und Aktivitäten möchten wir kurz vorstellen: Im Rahmen eines Austauschprogrammes der GDCh und der Northeastern Section of the American Chemical Society (NSACS), besuchten uns amerikanischen Austauschstudenten, die ebenfalls die jährliche JCF-Tagung, das Frühjahrssymposium in Kiel besuchten. Gemeinsam besichtigten wir das Shell Technology Center im Süden Hamburgs, und pflegten die transatlantischen Beziehungen während einer Hafenrundfahrt und dem Besuch des Brauhauses Gröninger, wo der Tag dann mit German Beer und deftigem bayrischem Essen ausklang. Um schon bei den Kleinsten die Begeisterung für das Entdecken und Hinterfragen von Beobachtungen zu wecken, besuchen wir mit Versuchen aus der Young Spirit Initiative, die in Kooperation mit Evonik entstanden ist, regelmäßig Kindergärten in Hamburg. Dort wird dann ein Liebesbrief chromatographisch untersucht, Schätze werden geborgen und Feuerlöscher gebaut. Die Begeisterung bei allen ist groß und die Anfragen von weiteren Kindergärten sprechen für sich. Neben den regelmäßigen Treffen in unserem JCF ist auch der Austausch zwischen den Regionalforen wichtig: Die bereits erwähnte jährliche Tagung, das Frühjahrssymposium, das Sprechertreffen im Herbst sowie Exkursionen und Veranstaltungen mit anderen Regionalforen stehen auf unserer Agenda. So sind wir in ständigem Austausch mit dem JCF-Kiel, aber auch das JCF-Würzburg war vor Kurzem bei uns zu Besuch und wir haben gemeinsam das DOW-Werk in Stade besichtigt. Einmal im Jahr organisieren wir in Zusammenarbeit mit dem Fachschaftsrat das Infogrillen am Fachbereich Chemie. Diese Veranstaltung soll dazu dienen, Studierende und Promovierende näher zusammen zu bringen und den Austausch im Fachbereich zu fördern. Es kann sich über die Themen der verschiedenen Arbeitskreise informiert werden und auch die Doktoranden untereinander können sich über ihre Projekte austauschen. Zudem bieten wir Nachwuchswissenschaftlern und externen Arbeitsgruppen die Möglichkeiten sich im Rahmen von Vorträgen zu präsentieren. Darüber hinaus laden wir regelmäßig Referenten aus verschiedenen chemischen Bereichen für Vorträge an den Fachbereich ein. Dabei legen wir Wert darauf die Themen ansprechend zu präsentieren, um ein möglichst breites Publikum zu erreichen. Weitere Informationen über unserer Aktivitäten findet Ihr auf Gerne könnt ihr euch auch unter direkt an uns wenden.