Organischer Teil (Woche 1-2): 1. Herstellung eines Alkens über die Olefinierung eines Aldehyds nach Wittig oder Wadsworth-Horner-Emmons.

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1 Organischer Teil (Woche 1-2): 1. Herstellung eines Alkens über die Olefinierung eines Aldehyds nach Wittig oder Wadsworth-Horner-Emmons. Jede Zweiergruppe stellt eines von zwei ausgewählten 2-zweistufigen Präparaten über eine Olefinierungsreaktion her. Alle Einzelversuche sind ausführlich beschrieben im Praktikum Präparative Organische Chemie (s.u.). a) 2-26, dann 11-3: Wittig-Reaktion zu 2,3 trans-4e-5,9-dimethyldeca-2,4,8- triensäureethylester, ausgehend von Bromessigester. 2 Stufen: Phosphoniumsalz und Ylid, dann Olefin. b) 2-28, dann 11-7: Wadsworth-Horner-Emmons-Olefinierung zu trans-3(4- Bromphenyl)acrylsäureethylester, ausgehend von Bromessigester. 2 Stufen: Arbuzow-Reaktion zum Phosphonat, dann Olefin. In beiden Fällen wird das Zwischenprodukt (Phosphoniumsalz und Ylid bzw. Phosphonat) isoliert. Charakterisierung mit 1 H-NMR und 31 P-NMR-Spektrum. Welche Signale stehen für das Phosphoniumsalz, welche für das Ylid und welche für das Phosphonat? Das Produkt der Olefinierung entsteht prinzipiell als E/Z-Gemisch (besonders bei der Wittig-Olefinierung). Es wird in beiden Fällen mittels Säulenchromatographie gereinigt. Die beiden Diastereomere (Reinprodukt oder eine Mischfraktion) sollen im 1 H-NMR-Spektrum voneinander unterschieden werden, evtl. unterstützt durch ein HPLC-Chromatogramm. Welches E/Z-Verhältnis wurde in der Reaktion insgesamt erreicht? Wie rein sind die erhaltenen Produktfraktionen? Lit.: R. Brückner et al., Praktikum Präparative Organische Chemie, Organisch- Chemisches Grundpraktikum, Spektrum Verlag Hier findet sich weitere Originalliteratur. 2. Herstellung eines β-ketiminat-liganden für die ringöffnende Lactidpolymerisation (integrierter Versuch Woche 5). Jede Zweiergruppe stellt eines von zwei Ketiminaten aus Acetylaceton und einem unsymmetrischen N,N-Dialkyldiamin her. 1

2 a) Acetylaceton + N,N-Diethyl(ethylendiamin) b) Acetylaceton + N,N-Dimethyl(propylendiamin) Das Produkt wird über sein 1 H-NMR-Spektrum (evtl. in Einzelfällen über sein Massenspektrum) charakterisiert. Es muss für die nachfolgende Komplexierung sauber und trocken sein. Lit.: D. Neculai, H. W. Roesky, A. M. Neculai, J. Magull, H.-G. Schmidt, M. Noltemeyer, J. Organomet. Chem. 2002, , Herstellung eines Bis(cylopentadiens) über das metallierte Dien Ausgangspunkt für Ansametallocene zur Olefinpolymerisation. Jede Zweiergruppe stellt eines von zwei Bis(cyclopentadienen) über Metallierung und Alkylierung des Dienvorläufers her. a) Inden + Dibromethan b) Cyclopentadien + Dimethyldichlorsilan Das Produkt wird über sein 1 H-NMR-Spektrum charakterisiert. Lit.: a) H. G. Alt, R. Ernst, I. K. Böhmer, J. Organomet. Chem. 2002, 658, ; b) Q. Yang, M. D. Jensen, Synlett 1996, Herstellung eines Tetrapeptids über Festphasensynthese. Jede Zweiergruppe stellt eines von zwei Tetrapeptiden an der festen Phase her. a) H-Tyr-Ile-Lys-Leu-OH b) H-Lys-Tyr-Lys-Leu-OH 2

3 Das Peptid wird aus Fmoc-Aminosäuren am Wang-Harz hergestellt. Nach der letzten Kupplung und Fmoc-Abspaltung wird das fertige Peptid mit TFA vom Harz abgespalten; dabei werden gleichzeitig sämtliche Schutzgruppen entfernt. Das Peptid wird in Ether gefällt, getrocknet und per 1 H-NMR-Spektrum und HPLC auf seine Identität und Reinheit hin überprüft. Lit.: W. Chan (Autor), W. C. Chan (Herausgeber), Peter D. White. In: Fmoc Solid Phase Peptide Synthesis: A Practical Approach (Taschenbuch), Oxford University Press Oxford New York 2000, ISBN

4 3. Praktikumswoche (Triphenyl-..\5_phosphanyliden)essigsäureethylester 1) Et02C'v"Br PPh3. [Et02C'v"~Ph3 Br 8 ] NaOH, H 2 0 Et02C~PPh3 C4H7Br02 (167.00) C22H2102P (348.37) Durchführung der Reaktion Im Reaktionskolben wird Triphenylphosphan (26.2 g, 100 mmol, 1.0 Äquiv.) in getrocknetem Toluol (120 ml) gelöst. Unter Rühren wird eine Lösung von Bromessigsäureethylester (Präparat 6-12, 16.7 g, 100 mmol) in getrocknetem Toluol (20 ml) zugetropft und danach über Nacht bei Raumtemp. gerührt. Der Niederschlag wird abgesaugt, mit etwas Petrolether (Sdp C) angefeuchtet und trocken gesaugt. Das rohe Phosphoniumbromid wird in eiskaltem H 2 0 (1 L) gelöst und unter Rühren so viel wässrige NaOH-Lösung (2 M) zugetropft, bis ein zuvor hinzugefügter Tropfen ethanolischer Phenolphthalein-Lösung gerade einen Farbumschlag auftreten lässt. Isolierung und Reinigung Der Niederschlag wird abgesaugt, mit Hp gewaschen, mit (wenig!) MeOH ~ angefeuchtet,.trocken gesaugt und in einer Trockenpistole bei 50 C über P 4 0,o,~O ehgetrocknet. Die Tltelverbmdung (85-90%) wird als farbloser Feststoff erhalten 2). Charakterisierung Schmp C. - 'H-NMR (400 MHz, CDCI 3 ) : 8 = 1.25 (t, 3H, CH J ), 3.34 (d, IH, CH), 4.43 (q, 2H, CH 2 ), (m, 9H, Ar-H), ppm (m, 6H, Ar-H). Anmerkungen: I) (Triphenyl-I,S-phosphanyliden)essigsäureethylester wird im Versuch 11-3 als Edukt eingesetzt. 2) Sollte der Schmelzpunkt nicht im angegebenen Bereich liegen, wird aus Et,O oder AcOEt umkristallisiert. M. Hanack, C. 1. Collins, H. Stutz, B. M. Benjamin,J. Am. ehern. Soc. 1981,103,

5 3. Praktikumswoche (Diethoxyphosphoryl)essigsäureethylester 1) P(OEth CaH170SP (224.19) Durchführung der Reaktion 2) Im Reaktionskolben wird ein Gemisch aus Triethylphosphit (30.7 g, 185 mmol, 1.23 Äquiv.) und Bromessigsäureethylester (Präparat 6-12,25.1 g, 150 nunol) 8 h unter Rückfluss erhitzt ]). Ableitungsschlauch Isolierung und Reinigung Nach dem Erkalten wird das entstandene Bromethan mit einer Destillationsapparatur bei Atmosphärendruck abdestilliert und der Rückstand im Vakuum fraktionierend destilliert (SdP'IOmbM I C). Die Titelverbindung (90-95%) wird als farblose Flüssigkeit erhalten. Charakterisierung IH-NMR (250 MHz, CDCI]): /) = 1.33 (me, 9H, 3 x CH 3 ), 2.96 (d, 2H, CH 2 ), 4.17 ppm (me, 6H, 3 x CH 2 ). Anmerkungen: I) (Diethoxyphosphoryl)essigsäureelhylester wird in den Versuchen 2-30, 11-7 und als Edukt eingesetzt. 2) Vorsicht: Bei der Reaktion wird Bromethan gebildet, das unter den Reaktionsbedingungen entweichen könnte. Daher muss am Blasenzähler ein Gasableirungsschlauch angebracht werden. 3) Die Reaktion kann auch über Nacht durchgefilhrt werden. Methode: A. van der Klei, R. L. P. de Jong, J. Lugtenburg, A. G. M. Tielens, Eur. J. Org. ehern. 2002,

6 296 Kapitel 11 Kondensationen von Phosphor-stabilisierten C-Nucleophilen trans,4E-5,9-Dimethyldeca-2,4,8- triensäureethylester ~o Durchführung der Reaktion Im Reaktionskolben wird ein Gemisch aus E-Citral l ) (Geranial, 1.52 g, 10.0 mrnol) und (Triphenyl-A. 5 -phosphanyliden)essigsäureethylester (Präparat 2-26, 3.48 g, 10.0 mmol, 1.0 Äquiv.) in getrocknetem Toluol (35 ml) 5 h bei 40 C gerührt. Das Reaktionsgemisch wird danach über Nacht bei Raumtemp. gerührt. Isolierung und Reinigung Das Lösungsmittel wird bei vermindertem Druck am Rotationsverdampfer entfernt. Der Rückstand wird mit Petrolether (Sdp C, 2 x 5 ml) digeriert und jeweils abgesaugt ' ). Die Filtrate werden vereinigt. Das Lösungsmittel wird bei vermindertem Druck am Rotationsverdampfer entfernt und der Rückstand durch Säulenchromatographie an Kieselgel (Säulendurchrnesser: cm, Eluens: CyclohexanJAcOEt, 95:5 v:v bis 90: I 0 v:v) gereinigt. Die Titelverbindung (50-55%) wird als farblose Flüssigkeit erhalten ). Charakterisierung n-:j = IH-NMR (250 MHz, CDCI): Ö= 1.30 (t, 3H, CH), 1.61 und 1.69 (s, 2 x 3H, 2 x CH), 1.90 (s, 3H, CH), 2.15 (me, 4H, 2 x CH,), 4.21 (q, 2H, CH,), 5.08 (m, IH, s~-h), 5.79 (m, lh, sp'-h), 6.00 (d, IH, s~-h), 7.55 ppm (me, I H, sp' -H). Anmerkungen: I),,z-Citral" trägt im Gegensatz dazu nur einen Trivialnarnen, nämlich Neral. 2) Diese zweimalige Maßnahme dient zum Entfernen des Triphenylphosphanoxids. 3) Das gereinigte Produkt kann das 2 Jcis,4E-Isomer zu 10% enthalten. In Anlehnung an: A. Gäbler, W. Boland, U. Preiss, H. Simon, Helv. Chim. Acta 1991, 74,

7 11. Praktikumswoche, 1. Teil 301 trans-3-(4-bromphenyl)acrylsäureethylester 1) ~o Sr ~ o 11 (EtOhP""C02Et, NaH in Mineralöl Durchführung der Reaktion 2) Im Reaktionskolben wird Natriumhydrid (60%ig in Mineralöl, 780 mg, 20.0 mmol, 1.33 Äquiv.) vorgelegt und mit getrocknetem THF (20 ml) versetzt. Unter Rübren und Eiskühlung wird eine Lösung von (Diethoxyphosphoryl)essigsäureetbylester (Präparat 2-28, 4.26 g, 19.0 mmol, 1.27 Äquiv.) in getrocknetem THF (10 ml) innerhalb von 10 min zugetropft. Anschließend wird unter fortgesetztem Rübren und Kühlen eine Lösung von 4-Brombenzaldehyd (2.78 g, 15.0 mmol) in getrocknetem THF (10 ml) innerhalb von 10 min zugetropft. Dann lässt man das Reaktionsgemisch auf Raumtemp. erwärmen und ruhrt noch I h bei Raurntemp. Isolierung und Reinigung Das Reaktionsgemisch wird mit wässriger N<l:iC03-Lösung (10%ig, 40 ml) versetzt, die organische Phase abgetrennt und die wässrige Phase mit I-BuOMe (3 x 40 rnl) extrahiert. Die vereinigten organischen Phasen werden mit Hp (3 x 20 ml) gewaschen und über N<l:iS04 getrocknet. Das Lösungsmittel wird bei vennindertem Druck am Rotationsverdampfer entfernt und der Rückstand durch Säulenchromatographie an Kieselgel (Säulendurchmesser: cm, Eluens: CyciohexanlAcOEt, 95:5 v:v bis 90: 1 0 v:v) gereinigt. Die Titelverbindung (70-75%) wird als farblose Flüssigkeit erhalten. Charakterisierung IH-NMR (250 MHz, CDCI,): 8; 1.32 (t, 3H, CH 3 ), 4.28 (q, 2H, C~), 6.42 (d, J = 16 Hz, IH, olefm. H), 7.36 (me, 2H, Ar-H), 7.51 (me, 2H, Ar-H), 7.61 ppm (d, J = 16 Hz, IH, olefin. H). Anmerkungen: I) Irans-4-Bromzimtsäureethylester. 2) Die Reaktion muss unter Feuchtigkeitsausschluss durchgefuhrt werden (apparative und labortechnische Details siehe Seite 50). O. Chuzel, O. Piva, Synlh. Commun. 2003, 33,

8 Journal of Organometallic Chemistry (2002) Synthesis and structure of monomeric and solvent-free LPrX 2 compounds supported by a new -diketiminato ligand [L=Et 2 NCH 2 CH 2 NC(Me)CHC(Me)NCH 2 CH 2 NEt 2,X=Cl, Br, BH 4 ] Dante Neculai, Herbert W. Roesky *, Ana Mirela Neculai, Jörg Magull, Hans-Georg Schmidt, Mathias Noltemeyer Institut für Anorganische Chemie, Uni ersität Göttingen, Tammannstraße 4, D Göttingen, Germany Received 29 May 2001; accepted 6 July 2001 Dedicated to Professor François Mathey on the occasion of his 60th birthday Abstract Trivalent praseodymium complexes with a new -diketiminato ligand, possessing two pendant arms, LPrX 2,(X=Cl (3), Br (4), BH 4 (5)), have been prepared by the reactions of the lithium salt of the ligand with the corresponding halides. X-ray structural and elemental analysis showed that 3, 4, and 5 are neutral, monomeric and solvent-free complexes. These complexes adopt a pseudo-octahedral geometry with the two X (X=Cl, Br, BH 4 ) arranged in the trans positions Elsevier Science B.V. All rights reserved. Keywords: -Diketiminato ligand; Lanthanide; Halides; Borohydride 1. Introduction Nitrogen-based ligands for preparing lanthanide complexes have been used increasingly over the past few years [1 7]. A broad range of chemistry of lanthanide complexes and important applications have also been described [8 10]. Nevertheless, there are only a few lanthanide complexes known with monoanionic -diketiminato ligands [9 12]. Our interest in the chemistry of diorganolanthanide complexes of general formula LLnR 2 stems from the potential use of these systems as novel olefin polymerization catalysts [13], and as -diketiminato-based ligands [14 16]. This led us to prepare some new starting materials. Consequently, given the importance of a solvent-free and bifunctional compound such as LLnX 2 as precursor for the synthesis of dialkyllanthanide complexes, we designed and synthesized a new -diketiminato ligand * Corresponding author. Tel.: ; fax: address: (H.W. Roesky). with two pendant donor arms, which proved to be suitable for our purpose. Herein, we report the synthesis of the ligand L= Et 2 NCH 2 CH 2 NC(Me)CHC(Me)NCH 2 CH 2 NEt 2 (2 H) and the preparation of LPrX 2,(X=Cl (3), Br (4), BH 4 (5)), derivatives. To the best of our knowledge, we obtained and characterized the first nonmetallocene, neutral, monomeric and solvent-free lanthanide compounds (LLnCl 2, LLnBr 2 and LLn(BH 4 ) 2 ) by X-ray structural analysis. Moreover, we demonstrated that LLnCl 2 could be used in metathesis reaction with NaBH Results and discussion 2.1. Synthesis of LH (2) LH was prepared in a two-step synthesis as shown in Scheme 1. Acetylacetone reacted with N,N-diethyl(ethylenediamine) in 1:1 molar ratio giving 1 in a very high yield X/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S X(01)01107-X

9 48 D. Neculai et al. / Journal of Organometallic Chemistry (2002) Scheme 1. Compound 1 is the intermediary step for the preparation of 2. Treatment of 1 with Meerwein salt, [Et 3 O]BF 4, in dichloromethane followed by N,N-diethyl(ethylenediamine) and NaOH afforded 2 in 52% yield. Compound 2 is a yellow oil at room temperature and soluble in any common organic solvent. It can be easily transformed into its lithium salt with LiMe (Eq. (1)), but attempts to solidify or to crystallize the LiL were unsuccessful. Therefore, every time when LiL was needed, it was prepared prior to use, and it was used without any further purification. LH+LiMe LiL (1) 2 CH Synthesis of LPrX 2, (X=Cl (3), Br (4), BH 4 (5)) Treatment of LiL with an equivalent amount of either anhydrous PrCl 3 or anhydrous PrBr 3 in toluene at refluxing temperature afforded LPrX 2 (X=Cl, Br), in good yields (Eq. (2)). LiL+PrX 3 LPrX 2 X=Cl (3), Br (4) (2) LiX Reaction of LPrCl 2 with an excess of NaBH 4 (1:3) in toluene under reflux afforded compound 5 (Eq. (3)) in moderate yield. LPrCl 2 +2NaBH 4 LPr(BH 4 ) 2 (3) 2NaCl 5 It has to be noticed that compounds 3 and 4 were prepared using the anhydrous salts, not the THF adducts. Compounds 3, 4, and 5 are well soluble in toluene, acetonitrile and THF. These complexes are thermally very stable, their melting points are in the range of C. Mass spectroscopy and elemental analysis showed that compounds 3, 4, and 5 are monomeric, solvent-free compounds, and contain no lithium halides. The monomeric structures of 3, 4, and 5 were confirmed by the single-crystal X-ray structural analysis. A 1 H-NMR resonance was not observed in every case due to the paramagnetic nature of the praseodymium. Compound 5 exhibits a 11 B-NMR spectrum that showed one sharp resonance at room temperature. This suggests that there is either a rapid exchange of the BH 4 groups on the NMR timescale, or both BH 4 groups are equivalent. A temperature-dependent NMR spectrum indicated that both BH 4 groups are equivalent in solution. Moreover, any coupling between 11 B and 1 H nuclei was not observed in the 11 B-NMR spectrum X-ray structural analysis of LPrX 2 (X=Cl (3), Br (4) and BH 4 (5)) Single crystals of 3 and 4 suitable for X-ray structural analysis were obtained by recrystallization from toluene, while single crystals of 5 were formed when the solvent was slowly removed in vacuo. Compounds 3, 4, and 5 crystallize in the monoclinic P2 1 /c space group. X-ray structural analysis revealed that compounds 3, 4, and 5 are monomeric in the solid state. The X-ray crystal structure of 4 resembles that of 3, therefore, only the X-ray crystal structure of 3 is given (Fig. 1). The crystal structure of 5 is given in Fig. 2. Selected bond distances and angles for compounds 3, 4, and 5 are listed in Table 1. In all compounds, both pendant arms are coordinated to the metal center and all four nitrogen atoms and the praseodymium atom are in the same plane. Moreover, for compound 4, the praseodymium atom is arranged in the plane of the Fig. 1. Perspective view of molecule 3 in the crystal.

10 D. Neculai et al. / Journal of Organometallic Chemistry (2002) in the range of the previously reported Pr B bond lengths of related compounds (2.757 A ) [21] Conclusions Fig. 2. Perspective view of molecule 5 in the crystal. Table 1 Selected bond lengths (A ) and bond angles ( ) for 3, 4, and 5 X Bond lengths Pr(1) N(2) 2.442(2) 2.462(2) 2.421(4) Pr(1) N(1) 2.448(2) 2.455(2) 2.430(4) Pr(1) N(3) 2.692(2) 2.688(2) 2.739(4) Pr(1) N(4) 2.694(2) 2.682(2) 2.749(5) Pr(1) X(1) (7) 2.852(1) 2.644(8) Pr(1) X(2) Bond angles N(2) Pr(1) N(1) (7) 75.79(8) 2.868(1) 77.18(7) 2.824(5) 76.66(14) N(2) Pr(1) N(4) 67.81(7) 69.89(7) 67.17(15) Pr(1) N(1) C(1) 126.3(2) (17) 124.7(4) N(1) C(1) C(2) 123.9(2) 125.3(2) 124.2(5) C(1) C(2) C(3) 130.6(3) 131.4(2) 130.8(5) C(2) C(3) N(2) 124.5(3) 125.2(2) 124.2(5) C(3) N(2) Pr(1) 125.6(2) (17) 122.9(4) N(3) Pr(1) N(4) (7) (6) (14) N(1) Pr(1) N(3) 69.26(8) 70.31(7) 68.57(14) X(1) Pr(1) X(2) (3) (12) 144.1(2) ligand framework, C 3 N 2 (see Table 1). For compounds 3 and 5, the praseodymium atom is positioned slightly out of this plane. The coordination number at the praseodymium atom in 3 and 4 is six and the geometry around the metal atom is pseudo-octahedral. The Pr N bond lengths of the pendant arm are longer than those of the backbone, due to the coordinative and covalent character involved in different bonding modes. The Pr X (X=Cl, Br) bond length is similar to those found in the literature (X=Cl, 2.896, A ) [6,17 20], (X=Br, 2.877, A ) [19,20]. The coordination number of the praseodymium atom in 5 is 10. Each BH 4 group is coordinated via three hydrogen atoms to the praseodymium atom. The Pr B bond lengths are different (Table 1). However, they are Herein, we have shown that compounds with the general formula LLnX 2 are easily available when - diketiminato-based ligands, and metals in the +3 oxidation state are used. However, the metathesis to yield LLnR 2 compounds is one of the important challenges in this field. Compounds LLnR 2 resemble those of the well-known catalysts of the titanium congeners. Up to this date, only aryl [10,11], or alkyl [12,13] groups without donor functions were used as substituents at the nitrogen atoms of the -diketiminato backbone in lanthanide chemistry. Thus, in order to increase their thermodynamic stability, we designed and obtained a ligand that contains two pendant arms on the nitrogen atoms, instead. This results in additional chelates, formed around the metal atom to yield monomeric and solvent-free complexes. 3. Experimental All operations involving air- and moisture-sensitive compounds were performed using standard Schlenk line and dry box techniques under purified nitrogen atmosphere. Toluene, Et 2 O, pentane, and CH 2 Cl 2 were dried from appropriate drying agents (Na/K alloy (toluene, pentane), Na/benzophenone (Et 2 O), CaH 2 (CH 2 Cl 2 )) and distilled under nitrogen prior to use. Benzene and hexane were used as received. N,N-diethyl(ethylenediamine) and water-free PrCl 3 were purchased from Aldrich and were used as received. Acetylacetone was distilled prior to use. [Et 3 O]BF 4 was prepared as described in the literature and used as solution in CH 2 Cl 2 [22]. C 6 D 6 and C 7 H 8 were dried over Na/K alloy and degassed H-, C- and 11 B-NMR spectra were recorded using Bruker AM 200. Chemical shifts are reported in units downfield from Me 4 Si with the solvent as the reference signal. Mass spectra were recorded using a Finnigan MAT 8230 instrument, and elemental analyses were carried out at the Analytical Laboratories of the Institute of Inorganic Chemistry of the University of Göttingen. Melting points were determined in sealed capillary tubes under nitrogen and are uncorrected Preparation of LH (2) Preparation of 1 In a 500 ml round-bottomed flask equipped with a condenser, 29.3 g (0.29 mol) of acetylacetone and 34 g (0.29 mol) of N,N-diethylenediamine in 250 ml of benzene were refluxed for 2 days. Consequently, the solvent

11 50 D. Neculai et al. / Journal of Organometallic Chemistry (2002) was removed and 1 distilled, as yellowish oil under dynamic vacuum (4.2 mbar). Yield 54.7 g (95%). 1 H- NMR (C 6 D 6, 200 MHz): 11.1 (s, 1H), 4.86 (s, 1H), 2.8 (q, 2H, J=5 Hz), 2.2 (m, 6H), 1.97 (s, 3H), 1.51 (s, 3H), 0.86 (t, 6H, J=7 Hz). 13 C-NMR (C 6 D 6, 125 MHz): , , 95.19, 53.19, 47.55, 41.80, 28.90, 18.70, Anal. Found: C, 66.53; H, 11.21; N, Calc. for C 11 H 22 N 2 O: C, 66.62; H, 11.18; N, 14.13%. EIMS; m/z (relative intensity): 198 ([M + ], 4), 112 ([M + C 5 H 12 N], 2), 86 ([C 5 H 12 N], 100) Preparation of 2 A 500 ml Schlenk flask topped with a 100 ml addition funnel was charged with 30 g (0.15 mol) of 1 in dry CH 2 Cl 2 (150 ml). A solution of [Et 3 O]BF 4 (54.1 g, 53.2%) in CH 2 Cl 2 was transferred by a cannula to the addition funnel and was added dropwise to the stirring reaction mixture over a period of 1 h. Then, the reaction was allowed to proceed for one additional hour at room temperature (r.t.). Consequently, g of N,Ndiethylenediamine in 50 ml CH 2 Cl 2 was syringed into the reaction mixture over a period of 30 min. Furthermore, stirring was continued overnight to ensure complete reaction. The solvent was removed and 6.05 g (0.15 mol) of NaOH in water (150 ml) and hexane (250 ml) was added. Using a separating funnel, the organic part was separated, washed with water (150 ml), dried over MgSO 4, concentrated and distilled under dynamic vacuum (4.2 mbar) to give 2 as yellow oil. Yield 23.3 g (52%). 1 H-NMR (C 6 D 6, 200 MHz): 11.3 (s, 1H), 4.55 (s, 1H), 3.28 (t, 4H, J=6.7 Hz), 2.63 (t, 4H, J=6.7 Hz), 2.45 (q, 8H, J=7 Hz), 1.73 (s, 6H), 0.97 (t, 12H, J=7.1 Hz). 13 C-NMR (C 6 D 6 ): , 95.04, 55.07, 47.84, 45.97, 19.44, Anal. Found: C, 68.82; H, 12.23; N, Calc. for C 17 H 36 N 4 : C, 68.87; H, 12.24; N, 18.90%. EIMS; m/z (relative intensity): 296 ([M + ], 7), 210 ([M + C 5 H 12 N], 36), 114 ([C 6 H 14 N 2 ], 100), 86 ([C 5 H 12 N], 78) Preparation of 3 Dry Et 2 O (50 ml) was added to 3.0 g (10.1 mmol) of 2 in a 100 ml Schlenk flask. The mixture was cooled to 78 C and a solution of 6.32 ml (1.6 M, 10.1 mmol) LiMe in Et 2 O was added dropwise. The reaction was stirred for 2 h at 78 C, and then stirred overnight at r.t. till the methane evolution had ceased. The solvent was removed and toluene (30 ml) was added. Finally, the solution was added dropwise to a suspension of 2.50 g (10.1 mmol) PrCl 3 in toluene (30 ml) in a 100 ml Schlenk flask. Then, the reaction mixture was refluxed overnight. The suspension was filtered, concentrated until crystals are formed. Finally, the resulting solution was warmed and it was left undisturbed for several hours at r.t. The large yellow crystals that formed were separated by filtration, washed with pentane (50 ml), and dried in vacuo. Yield 7.61 g (88.2%). M.p. 164 C. Anal. Found: C, 40.53; H, 6.95; N, Calc. for C 17 H 35 Cl 2 N 4 Pr: C, 40.25; H, 6.95; N, 11.04%. EIMS; m/z (relative intensity): 506 ([M + ], 12), 471 ([M + Cl], 7), 420 ([M +, C 5 H 12 N], 100) Preparation of 4 Compound 4 was obtained by a method analogous to the preparation of 3. DryEt 2 O (20 ml) was added to 0.58 g (1.98 mmol) of 2 in a 25 ml Schlenk flask. The mixture was cooled to 78 C and a solution of 1.3 ml (1.6 M, 2 mmol) LiMe in Et 2 O was added dropwise. The reaction was stirred for 2 h at 78 C and then stirred overnight at r.t. Then, the volatiles were removed in vacuo and toluene (15 ml) was added. This solution was added dropwise to a suspension of 0.75 g (1.98 mmol) PrBr 3 in toluene (20 ml). Finally, the reaction mixture was refluxed overnight. The suspension was filtered, concentrated until crystals were formed. The resulting solution was warmed and it was left undisturbed for several hours at 26 C. The yellow crystals that formed were recovered by filtration, washed with pentane, and dried in vacuo. Yield 0.89 g (75.4%). M.p. 188 C. Anal. Found: C, 34.25; H, 5.93; N, Calc. for C 17 H 35 Br 2 N 4 Pr: C, 34.25; H, 5.92; N, 9.40%. EIMS; m/z (relative intensity): 596 ([M + ], 5), 515 ([M + Br], 3), 510 ([M + C 5 H 12 N], 30), 86 ([C 5 H 12 N], 100) Preparation of 5 A mixture of 0.5 g (0.98 mmol) 3 and g (2.96 mmol) NaBH 4 in a 50 ml Schlenk flask equipped with a condenser was refluxed in toluene (35 ml) overnight. The suspension was filtered. The resulting clear solution was concentrated under reduced pressure to obtain yellow crystals of 5, which were collected by filtration and washed with pentane (10 ml). Yield 0.31 g (68%). M.p. 142 C. 11 B-NMR (C 7 D 8 /ext. BF 3 OR 2,25 C): 67.2 (s). Anal. Found: C, 43.56; H, 9.08; N, Calc. for C 17 H 43 B 2 N 4 Pr: C, 43.81; H, 9.30; N, 12.02%. EIMS; m/z (relative intensity): 466 ([M + ], 4), 451 ([M + BH 4 ], 76), 366 ([M + (C 5 H 12 N+BH 3 )], 100). 4. X-ray crystallography Data for crystal structures of 3 and 5 were collected on a Stoe Siemens four-circle diffractometer, and data for the crystal structure of 4 were collected on a Stoe image plate IPDS II-system. All structures were solved by direct methods (SHELXS-97) and refined against F 2 using SHELXS-97 [23]. The heavy atoms were refined anisotropically. Hydrogen atoms were included using the riding model

12 D. Neculai et al. / Journal of Organometallic Chemistry (2002) Table 2 Crystal data and structure refinement parameters for compounds 3, 4, and Empirical formula C 17 H 35 Cl 2 N 4 Pr C 17 H 35 Br 2 N 4 Pr C 17 H 43 B 2 N 4 Pr Formula weight Temperature ( C) Wavelength (A ) Color Yellow Yellow Yellow Crystal system Monoclinic Monoclinic Monoclinic Space group P2 1 /n P2 1 /n P2 1 /n Unit cell dimensions a (A ) (2) (18) (12) b (A ) (10) (9) (16) c (A ) (3) (5) (3) ( ) ( ) 95.86(2) (15) (13) ( ) V (A 3 ) (6) (6) (6) Z D calc (g cm 3 ) Absorption coefficient (mm 1 ) Crystal size (mm) Theta range for data collection ( ) Index ranges 14 h 14, 12 k 13, 12 h 12, 8 k 9, 12 h 12, 11 k 13, 17 l l l 17 Reflections collected/unique / Reflections observed [I 2 (I)] 3891 [R int =0.0300] 3560 [R int =0.0794] 3680 [R int =0.0384] Data/restraints/parameters 3889/0/ /0/ /396/247 Final R indices [I 2 (I)] R 1 =0.0215, wr 2 = R 1 =0.0182, wr 2 = R 1 =0.0342, wr 2 = R indices (all data) R 1 =0.0222, wr 2 = R 1 =0.0202, wr 2 = R 1 =0.0421, wr 2 = Goodness-of-fit onf Largest difference peak and hole and and and (e A 3 ) with U iso tied to U iso of the parent atoms. Crystal data collection details, and the solution and refinement procedures are summarized in Table Supplementary material Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC nos , , and for compounds 3, 4 and 5, respectively. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: ; ccdc.cam.ac.uk or www: Acknowledgements We are thankful to the Deutsche Forschungsgemeinschaft for financial support. Moreover, we thank Ulrich Schaller for a sample of PrBr 3. References [1] F.T. Edelmann, Angew. Chem. 107 (1995) 2647 (Angew. Chem. Int. Ed. Engl. 34 (1995) 2466). [2] J.A.R. Schmidt, J. Arnold, J. Chem. Soc. Chem. Commun. (1999) [3] P.W. Roesky, Inorg. Chem. 37 (1996) [4] T. Dubbe, S. Gambarotta, G. Yap, Organometallics 17 (1998) [5] J.R. Hagadorn, J. Arnold, Organometallics 15 (1996) 984. [6] C. Apostolidis, A. Carvalho, A. Domingos, B. Kanellakopulos, R. Maier, N. Marques, A.P. de Matos, J. Rebizant, Polyhedron 18 (1999) 263. [7] S. Bambirra, M.J.R. Brandsma, E.A.C. Brussee, A. Meetsma, B. Hessen, J.H. Teuben, Organometallics 19 (2000) [8] R. Duchateau, C.T. Van Wee, A. Meetsma, J.H. Teuben, J. Am. Chem. Soc. 115 (1993) [9] L.W.M. Lee, W.E. Piers, M.R.J. Elsegood, W. Clegg, M. Parvez, Organometallics 18 (1999) [10] D. Dress, J. Magull, Z. Anorg. Allg. Chem. 621 (1995) 948. [11] P.B. Hitchcock, M.F. Lappert, S. Tian, J. Chem. Soc. Dalton Trans. (1997) [12] D. Dress, J. Magull, Z. Anorg. Allg. Chem. 620 (1994) 814. [13] G.J.P. Britovsek, V.C. Gibson, D.F. Wass, Angew. Chem. 111 (1999) 448 (Angew. Chem. Int. Ed. Engl. 38 (1999) 428). [14] Y.Q. Ding, H.W. Roesky, M. Noltemeyer, H.-G. Schmidt, Organometallics 20 (2001) 1190.

13 52 D. Neculai et al. / Journal of Organometallic Chemistry (2002) [15] C.M Cui, H.W. Roesky, H.-G. Schmidt, M. Noltemeyer, Angew. Chem. 112 (2000) 4705 (Angew Chem. Int. Ed. 39 (2000) 4531). [16] C. Cui, H.W. Roesky, H.-G. Schmidt, M. Noltemeyer, H. Hao, F. Cimpoesu, Angew. Chem. 112 (2000) 4444 (Angew. Chem. Int. Ed. 39 (2000) 4274). [17] Q. Shen, M. Qi, S. Song, L. Zhang, Y. Lin, J. Organomet. Chem. (1997) 549. [18] S.W.A. Bligh, N. Choi, H.R. Hudson, C.M. McGrath, M. McPartlin, J. Chem. Soc. Dalton Trans. (1994) [19] K. Kramer, G. Meyer, P. Fischer, A.W. Hewat, H.U. Gudel, J. Solid State Chem. 95 (1991) 1. [20] U. Schaller, Dissertation, Universität Göttingen, [21] D. Deng, X. Zheng, C. Qian, J. Sun, L. Zhang, J. Organomet. Chem 466 (1994) 95. [22] C.T. Goralski, W. Chrisman, D.L. Hasha, L.W. Nicholson, P.R. Rudolf, D. Zakett, B. Singaram, Tetrahedron 53 (1997) [23] G.M. Sheldrick, SHELXL: Program for Crystal Structure Refinement, University of Göttingen, Göttingen, Germany, 1997.

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16 Journal of Organometallic Chemistry 658 (2002) 259/265 Dinuclear ansa zirconocene complexes containing a sandwich and a half-sandwich moiety as catalysts for the polymerization of ethylene Helmut G. Alt *, Rainer Ernst, Ingrid K. Böhmer Laboratorium für Anorganische Chemie der Universität Bayreuth, Lehrstuhl für Anorganische Chemie II, Universität Bayreuth, Postfach , Universitaetsstrasse 30, NW I, D Bayreuth, Germany Received 16 May 2002; received in revised form 5 June 2002; accepted 14 June 2002 Abstract Dinuclear ansa zirconocene complexes containing a half-sandwich and a sandwich moiety and their ligand precursors have been synthesized and characterized. After activation with methylalumoxane (MAO), these catalysts produce polyethylenes with bimodal molecular weight distributions in homogeneous and heterogeneous media. The catalyst performances and the polymer properties were compared with mono nuclear reference catalysts. # 2002 Elsevier Science B.V. All rights reserved. Keywords: Ansa zirconocene; Half-sandwich complexes; Dual site catalysts; Dinuclear complexes; Homogeneous and heterogeneous ethylene polymerization 1. Introduction In the last decade metallocene complexes have been established as excellent catalysts for the polymerization of ethylene and propylene [1 /5]. The produced polyolefins have narrow molecular weight distributions due to identical active sites of the catalyst. However, this can be disadvantageous for industrial processing. In order to obtain broader molecular weight distributions, cumbersome or costly approaches, like the blending of different resins, are necessary. On the other side, in most cases, it is not possible to obtain the desired multi modal resins by mixing individual mono nuclear catalysts (averaging effect). Therefore, it was the intention to solve this problem with dinuclear complexes as catalyst precursors. Two different active sites in one molecule should be able to produce two different polymer chains with different molecular weights. Other known dinuclear complexes do not unify two different catalytic centers * Corresponding author. Tel.: / ; fax: / address: (H.G. Alt). [6 /13]. The model compounds presented in this paper should provide the advantages of both the half-sandwich (high molecular mass) [14,15] and the sandwich catalysts (low molecular mass) [5,16,17] and thus have the potential of dual site catalysts. 2. Results and discussion 2.1. Synthesis of the ligand precursors For the preparation of asymmetric dinuclear metallocene complexes, a ligand precursor with an v-alkenyl functionality is reacted catalytically with dichloromethylsilane in a hydrosilylation reaction [18]. This chlorosilane intermediate then reacts in an S N 2 reaction [19 /23] with two equivalents of sodium cyclopentadienide to form the ligand precursor (Scheme 1). In the same manner, the following intermediates and ligand precursors were synthesized: X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S X ( 0 2 ) X

17 260 H.G. Alt et al. / Journal of Organometallic Chemistry 658 (2002) 259/ Synthesis of the dinuclear complexes 7/9 The reaction of such a ligand precursor with four equivalents of butyllithium and two equivalents of zirconium tetrachloride leads to the dinuclear complexes 7/9 (Scheme 2). The following complexes were synthesized in the same manner: Compounds 7/9 showed mid range activities in the homogeneous polymerization which varied around the value for reference catalyst 11/methylalumoxane (MAO). The homogeneous polymerization with 9/ MAO exceeded the activity of the reference catalyst 11/MAO by ca. 50%. The activities from the heterogeneous experiments were generally lower than those from the homogeneous series. This result confirms the For comparison purposes, the already known silyl bridged sandwich complex 10 [20,23] (Scheme 3) and the half-sandwich complex 11 [14,15] (Scheme 4) were synthesized Polymerization of ethylene Half-sandwich catalysts of titanium and zirconium are known to produce polyethylenes of very high molecular masses (/10 6 g mol 1 ) [13,14]. In contrast, silyl bridged bis(cyclopentadienyl) catalysts produce resins with a significantly lower molecular mass ( B/ 5/10 5 g mol 1 ) [20,23]. The polymerization properties of the asymmetric dinuclear complexes 7 /9 meet the expectations (Table 1). observations from other metallocene catalysts [17,20,23] where heterogenization on silica gel causes decreasing activities (Scheme 5). The lowest decrease is observed in the case of the half-sandwich reference catalyst 11/ MAO. The molecular masses of these polyethylenes produced with the dinuclear catalysts 7 /9/MAO are significantly higher than those of the reference catalyst 10/MAO; the trend of the molecular weights by heterogenization was not found to follow a certain rule (Scheme 6). The polymer produced with catalyst 11/MAO shows the highest M n of the complete series both under homoand heterogeneous conditions. All other polymers vary around M n /80 kg mol 1 under homogeneous condi-

18 H.G. Alt et al. / Journal of Organometallic Chemistry 658 (2002) 259/ Table 1 Polymerization data Catalyst Activity g (PE)/g (Zr) h M n T m M w DH m M h Crystallinity a M z Polydispersity HI Homogeneous conditions 7 51,000 81, , ,654, , ,000 85, , ,098, , ,000 70, , ,983, , ,000 95,120 n.d. 266, , , , ,500 n.d. 737,200 1,981, , Heterogeneous conditions (supported on silica gel) 7 42,000 33, , ,679, , ,000 91, , ,417, , ,000 45, , ,329, , , ,000 n.d. 271,200 1,075, , , ,100 n.d. 488,300 2,008, , n.d., not determined. Scheme 1. Synthesis of the intermediate 1 and the ligand precursor 2. Scheme 2. Synthesis of the dinuclear complex 7. Scheme 3. Synthesis of the mono nuclear silyl bridged metallocene complex 10. Scheme 4. Synthesis of the mono nuclear amido silyl half-sandwich complex 11. tions. Silica supported catalysts develop molecular masses that are in the range of the homogeneously produced polymers or below (Scheme 6). Polymerization with the dinuclear complexes/mao gave resins with a broader molecular mass distribution width HI than with mononuclear complexes. The polydispersities observed were between HI /6.2 and

19 262 H.G. Alt et al. / Journal of Organometallic Chemistry 658 (2002) 259/265 Scheme 5. Activities of the catalysts 7 /11/MAO in the homogeneous and heterogeneous polymerization reactions of ethylene. at 25,000 g mol 1 by the sandwich component of catalyst 7. This conclusion can be derived from the properties of the monomeric reference catalysts and the produced polymers. The HT-GPC curve does not always show two separate maxima but a distinct broadening of the molecular mass distribution relative to the mononuclear catalysts. Polymerization with a 1:1 mixture of 10/MAO and 11/MAO does not give the same bimodal molecular weight distribution as with 9/MAO. The 1:1 mixture of 10/MAO and 11/MAO produces a mononuclear resin with only a slightly broadened molecular weight. We assume that in the mixture, the two originally different active sites communicate with each other, eventually via the cocatalyst MAO to give an averaged molecular weight. In the dinuclear catalysts, the active sites are separated from each other and cannot undergo such a reaction. This behavior is the major justification for the preparation of such dual site catalysts. Scheme 6. Molecular weights M n of the polyethylenes obtained from 7 /11/MAO. 3. Experimental Scheme 7. Polydispersities HI of the polyethylenes obtained from 7 / 11/MAO under homo- and heterogeneous conditions. They exceeded the values of the reference polymers of 10/ MAO (homogeneous: HI /2.8; heterogeneous: HI / 2.6) and 11/MAO (homogeneous: HI /2.8; heterogeneous: HI/2.5) by more than 100% (Scheme 7). This width increase is especially pronounced with the polyethylene produced from 7/MAO where two relative maxima can be seen in the HT-GPC plot (Scheme 8). It is well known from former results that halfsandwich catalysts produce polyethylenes with high molecular masses (/10 6 g mol 1 ) [13,14]. The amido silyl compounds are sterically not very demanding and the active center of the catalysts is easily accessible for the addition of the monomer. Polymer growth occurs stress free, termination reaction only starts at high molecular weight. It can be postulated that the fraction with a maximum at 700,000 g mol 1 is produced by the half-sandwich component, the fraction with a maximum All experimental work was routinely carried out using Schlenk technique. Dried and purified Ar was used as inert gas. Toluene, pentane, diethylether and tetrahydrofuran were purified by distillation over Na/K alloy. Ether was additionally distilled over LiAlH 4. Methylene chloride was dried with CaH 2. Deuterated solvents such as CHCl 3 -d 1 and C 6 H 6 -d 6 were dried over molecular sieves (300 pm), degassed and stored under inert gas atmosphere. Commercially available indene was distilled and stored at /28 8C. Cyclopentadiene was freshly distilled from the dimer. MAO (30% in C 6 H 5 CH 3 ) was supplied by Witco Company, Bergkamen. All the other starting materials were commercially available and were used without further purification NMR spectroscopy The spectrometer Bruker ARX 250 was available for the recording of the NMR spectra. The organometallic compounds were prepared under inert gas atmosphere (Ar). The spectra were recorded at 25 8C. The chemical shifts in the 1 H-NMR spectra are referred to the residual proton signal of the solvent (d/7.24 ppm for CHCl 3, d/7.15 ppm for C 6 H 6 ) and in the 13 C-NMR spectra to the solvent signal (d/77.0 ppm for CHCl 3 -d 1, d/128.0 ppm for C 6 H 6 -d 6 ). Tetramethylsilane (d/0.0 ppm) was used as external reference for 29 Si-NMR spectra.

20 H.G. Alt et al. / Journal of Organometallic Chemistry 658 (2002) 259/ Scheme 8. Molecular weight distribution of the polyethylene produced with 7/MAO under homogeneous conditions GC /MS and mass spectroscopy GC /MS spectra were performed with a HP5971A mass detector in combination with a HP5890 gas chromatograph. Helium was applied as carrier gas, a 12 m J&W Fused Silica column (DB 1, film 0.25 mm was used. The measuring program was: 3 min at 70 8C (starting phase); 20 8C min 1 (heating phase); variable time at 210 8C (final phase). The mass spectra were recorded with a VARIAN MAT CH7 instrument, GC/MS with a VARIAN 3700 gas chromatograph in combination with a VARIAN MAT 312 mass spectrometer Gas chromatography Gas chromatograms were recorded using a Perkin/ Elmer Auto System gas chromatograph with flame ionization detector (FID) and He as carrier gas (1 ml min 1 ). Temperature program: Starting phase: 3 min at 50 8C Heating phase: 5 8C min 1 (15 min) Plateau phase: 310 8C (15 min) of the styragels were 500, 1000, 10,000 and 100,000 Å in the individual columns. A RI Waters 401 refractometer was used for detection. The polymer samples were dissolved in boiling 1,2,4-trichlorobenzene that was also used as eluent. The measurements were carried out at 150 8C. The apparatus was calibrated with an internal polystyrene standard Synthesis of the chlorosilane precursors General procedure v-alkenyl substituted half-sandwich ligand precursor (10 mmol) in 10 ml of C 5 H 12 and ca. 50 mg of hexachloroplatinic acid hydrate were given to a Schlenk vessel at room temperature (r.t.). Methyldichlorosilane (1.15 g, 10 mmol) was added and the mixture was stirred for 40 h. Then the suspension was filtered through Na 2 SO 4 and the solvent was removed in vacuo. Yields: 90/95% Synthesis of the ligand precursors 1/ High temperature gel permeation chromatography (HT-GPC) A Waters HT-GPC 150C instrument was applied to measure the mass distributions of the polymer samples. Four columns filled with cross-linked polystyrene were used for separation of the fractions. The pore diameters General procedure The corresponding chlorosilane presursor (5 mmol) in 100 ml of Et 2 O was treated with 0.88 g (10 mmol) sodium cyclopentadienide dissolved in 10 ml of THF. The mixture was stirred for 8 h at r.t. The suspension was filtered through Na 2 SO 4 and the solvent was removed in vacuo. Yields: 90/95%.

21 264 H.G. Alt et al. / Journal of Organometallic Chemistry 658 (2002) 259/265 Table 2 NMR data of compounds 1 /9 Compound 1 H-NMR 13 C-NMR 29 Si-NMR /7.19 (m, 5H, ar H, Ind), 6.61 (s, 1H, ar H, Ind), 3.79 (s, 1H, al H, Ind), 2.03/0.57 (m, 12H, bridge), 0.91 (s, 3H, N Si CH 3 ), 0.78 (s, 9H, t Bu), 0.14 (s, 3H, Cl Si CH 3 ) /7.22 (m, 12H, ar H, Ind), 6.95/6.47 (m, 8H, ar H, Cp), 3.52 (s, 2H, al H, Ind), 3.06/3.00 (m, 2H, al H, Cp), 1.26/0.45 (m, 12H, bridge), 1.21 (m, 9H, t Bu), 0.02/ 0.10 (s, 6H, Si CH 3 ) /7.31 (m, 4H, ar H, Ind), 6.41 (s, 1H, ar H, Ind), 3.72 (s, al H, Ind), 2.76/2.71, 1.87/1.23 (m, 12H, bridge), 1.33 (s, 3H, N Si CH 3 ), 0.84 (s, 9H, t Bu), 0.29 (s, 6H, ClSiCH 3 ) /7.22 (m, 4H, ar H, Ind), 6.34 (s, 1H, ar H, Ind), 3.69 (s, 1H, al H, Ind), 2.68/0.54 (m, 20 H, bridge, pentylsubstituent), 0.91 (s, 3H, N Si CH 3 ), 0.79 (s, 9H, t Bu), 0.18 (s, 6H, ClSiCH 3 ) /7.19 (m, 12H, ar H, Ind), 6.93/6.23 (m, 8H, ar H, Cp), 3.54 (s, 2H, al H, Ind), 3.02 (m, 2H, al H, Cp), 1.77/ 0.13 (m, 8H, bridge), 1.23 (s, 9H, t Bu), 0.07/0.26 (s, 9H, SiCH 3 ) /7.26 (m, 12H, ar H, Ind), 6.98/6.33 (m, 8H, ar H, Cp), 3.68 (s, 2H, al H, Ind), 3.01 (m, 2H, al H, Cp), 1.34/ 0.55 (m, 20H, bridge), 1.19/1.17 (m, 9H, t Bu), 0.05/ 0.13 (s, 6H, Si CH 3 ) /6.38 (m, 14H, ar H), 2.72/0.46 (m, 23H, bridge, pentyl-substituent), 1.33 (s, 9H, t Bu), 0.03, 0.15 (s, 6H, SiCH 3 ) /6.61 (m, 14H, ar H), 2.30/0.41 (m, 12H, bridge), 1.41 (s, 9H, t Bu), 0.11/0.01 (s, 6H, SiCH 3 ) /6.67 (m, 14H, ar H), 2.74/0.47 (m, 8H, bridge), 1.05 (s, 9H, t Bu), 0.21, 0.19, 0.01 (s, 9H, Si CH 3 ) 144.7, (C q, Ind), 131.5, 129.9, 126.6, 124.6, (CH, Ind), 44.9 (CH, al, Ind), 32.1, 30.0, 22.5, 21.8, 18.2, 14.2 (CH 2, bridge), 4.2 (CH 3, t Bu), 0.9, 0.2 (Si CH 3 ) 144.6, (C q, Ind, Cp), 138.5, 132.9, 129.6, 126.2, 124.5, (CH, ar, Ind, Cp), 47.3 (CH, al, Ind, Cp), 33.1, 29.9, 23.9, 22.9 (CH 2, bridge), 3.2, 4.5 (SiCH 3 ) 144.8, (C q, Ind), 127.8, 125.8, 124.6, 123.7, (CH, ar, Ind), 45.7 (CH, al, Ind), 33.5, 33.1 (CH 3, t Bu), 31.9, 27.5, 23.6, 19.9 (CH 2, bridge), 5.4, 0.3, 90.0 (SiCH 3 ) 145.1, 144.6, (C q, Ind), 127.5, 125.6, 124.4, 123.6, (CH, ar, Ind), 44.9 (CH, al, Ind), 32.5, 32.1, 28.4, 27.9, 22.7, 22.4, 21.7, 16.6 (CH 2, bridge, pentyl-substituent), 15.8 (CH 3, t Bu), 14.3 (CH 3 ), 1.4, 1.9 (SiCH 3 ) 145.7, (C q, Ind, Cp), 132.9, 129.3, 125.1, 124.1, 123.2, (CH, ar, Ind, Cp), 46.3 (CH, al, Cp), 32.5, 29.9, 27.6, 23.4 (CH 2, bridge), 4.6, 5.9 (Si CH 3 ) 144.9, (C q ), 137.3, 133.2, 127.8, 125.4, 124.7, (CH, ar, Ind, Cp), 46.4 (CH, al, Cp), 35.4, 32.6, 29.6, 24.3, 23.6, 22.8 (CH 2, bridge), 4.2, 5.9 (Si CH 3 ) 145.8, (C q, Ind, Cp), 138.3, 132.9, 130.9, 129.4, 125.1, 123.9, (CH, Ind, Cp), 45.9 (C q, t Bu), 33.2, 32.2, 29.9, 28.6, 27.6, 24.2, 24.1, 22.8, 13.4, 13.3 (CH 2, bridge, pentyl-substituent), 14.3 (CH 3, t Bu), 5.8, 6.7 (SiCH 3 ) 145.6, (C q, Ind, Cp), 131.0, 128.3, 126.4, 123.9, (CH, Ind, Cp), 32.2, 29.7, 27.1, 26.5, 24.3, 22.9 (CH 2, bridge), 4.5 (CH 3, t Bu), 1.9, 6.5 (Si CH 3 ) 145.8, (C q, Ind, Cp), 130.7, 128.6, 127.5, 124.7, (CH, Ind, Cp), 33.2, 32.9 ( t Bu), 30.8, 30.7, 27.4, 26.2, 19.8, 14.1 (CH 2, bridge), 0.3, 0.2, 6.5 (Si CH 3 ) 33.1 (Cl Si), 4.2 (Ind Si) 5.5, (Cl Si), 7.3 (Ind Si) 33.1 (Cl Si), 5.4 (Ind Si) , (CpSi), 9.5 (Ind Si) 7.6 (CpSi), 8.1 (Ind Si) 7.8 (CpSi), 12.9 (Ind Si) 3.7. Synthesis of the dinuclear complexes 7/ General procedure The ligand precursor (5 mmol) was dissolved in 400 ml of Et 2 O and 12.5 ml (20 mmol) of n-butyllithium (1.6 M in C 6 H 14 ) were added. The reaction mixture was stirred for a minimum of 8 h at r.t. The solution was cooled to /78 8C. Then 2.33 g (10 mmol) of ZrCl 4 was added. The reaction mixture was brought to r.t. within 6 h and stirred for another 6 h. The solvent was removed in vacuo, the residue suspended in CH 2 Cl 2 and the suspension filtered through Na 2 SO 4. The CH 2 Cl 2 phase was removed in vacuo, the residue washed with C 5 H 12 and the product crystallized from CH 2 Cl 2 /C 5 H 12. Yields: 60/70% (Table 2) Synthesis of the ligand precursors for the mono nuclear complexes General procedure Dichlorodimethylsilane (2.58 g, 20 mmol) in 200 ml of Et 2 O and 10 mmol of sodium cyclopentadienide (or 10 mmol of fluorenyllithium) were mixed at r.t. in a Schlenk vessel. The mixture was stirred for 8 h, then filtered through Na 2 SO 4 and silica gel. The solvent was removed in vacuo. Yield: 95% Preparation of the indenyl chlorosilane precursor Indene (80 mmol) in 150 ml of Et 2 O was treated with 50 ml (80 mmol) of butyllithium (1.6 M solution in C 6 H 14 ). The solution was stirred for 4 h at r.t. Then it was cooled to /78 8C. Dichlorodimethyl silane (80

22 H.G. Alt et al. / Journal of Organometallic Chemistry 658 (2002) 259/ mmol) was added, slowly warmed to r.t. and stirred for 12 h. The suspension was filtered through Na 2 SO 4 and the solvent was removed in vacuo. Yield: 95% Preparation of the indenyl ligand precursor The indenyl chlorosilane precursor (80 mmol) in 200 ml of CH 2 Cl 2 was treated with 200 mmol of t- butylamine at r.t. The mixture was stirred for 12 h, then the solvent was removed in vacuo. The residue was suspended in 200 ml of C 5 H 12 and the suspension was filtered through Na 2 SO 4. The solvent was removed in vacuo. Yield: 95% Preparation of the mono nuclear zirconocene complex 10 The ligand precursor (10 mmol) was dissolved in 200 ml of Et 2 O. Butyllithium solution (12.5 ml, 1.6 M in C 6 H 14 ; 20 mmol) was added. The mixture was stirred for at least 8 h at r.t. Then the solution was cooled to /78 8C and 2.33 g (10 mmol) of ZrCl 4 was added. The mixture was brought to r.t. within 6 h and stirred for another 6 h. The solvent was removed in vacuo, the residue was suspended in CH 2 Cl 2 and the suspension was filtered through Na 2 SO 4. The solvent of the CH 2 Cl 2 phase was removed in vacuo, the residue was washed with C 5 H 12 and Et 2 Oseveral times, dissolved in CH 2 Cl 2 and the solution was crystallized at /28 8C. Yields: 50/70% Synthesis of the amidosilyl zirconium complex 11 The ligand precursor (20 mmol) was dissolved in 400 ml of Et 2 O. Butyllithium solution (12.5 ml, 1.6 M in C 6 H 14 ; 20 mmol) was added at /78 8C. The mixture was stirred for 12 h at r.t. Then the solution was cooled to /78 8C again and 4.66 g (20 mmol) of ZrCl 4 was added. The mixture was brought to r.t. within 10 h and stirred for another 10 h. The solvent was removed in vacuo, the residue was suspended in C 5 H 12 and the suspension was filtered through Na 2 SO 4. The solvent was removed in vacuo, the residue was suspended in C 5 H 12 and the LiCl containing solution was filtered. The solution was stored for 24 h at /28 8C. The yellowish complex precipitated. Yield: 35% Polymerization reactions An amount of 20/25 mg of the corresponding complex was dissolved in 50 ml of C 6 H 5 CH 3.Avolume of the solution containing 1 /2 mg of complex was taken and activated with MAO (30% in C 6 H 5 CH 3 ;Al/Zr/ 2500:1). For heterogeneous polymerizations silica gel was added (1 g SiO 2 mmol 1 (Zr)) to this solution and the suspension was stirred for 3 min. Both for homogeneous and heterogeneous polymerizations, the catalyst suspension was diluted with 250 ml of C 5 H 12 and injected to a 1 l Büchi laboratory autoclave thermostated at 60 8C. An ethylene pressure of 10 bar was applied to the reactor and the catalyst was polymerized for 30 min at 60 (9/ 3) 8C. The obtained polymer was dried in air for at least 60 h. The polymerization results and the physical data of the polymers are presented in Table 1. Acknowledgements We thank the Deutsche Forschungsgemeinschaft (DFG) and Phillips Petroleum Company (Bartlesville, OK, USA) for the financial support and Witco company (Bergkamen) for the donation of methylalumoxane. References [1] (a) H.-H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, R. Waymouth, Angew. Chem. 107 (1995) 1255; (b) H.-H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, R. Waymouth, Angew. Chem. Int. Ed. Engl. 34 (1995) [2] M. Bochmann, J. Chem. Soc. Dalton Trans. (1996) 255. [3] F. Küber, Chem. Unserer Zeit 28 (1994) 197. [4] W. Kaminsky, J. Chem. Soc. Dalton Trans. (1998) [5] H.G. Alt, A. Köppl, Chem. Rev. 100 (2000) 1205 (and references therein). [6] W. Spaleck, F. Küber, B. Bachmann, C. Fritze, A. Winter, J. Mol. Catal. A 128 (1998) 279. [7] S. Ciruelos, T. Cuenca, P. Gómez-Sal, A. Manzanero, P. Royo, Organometallics 14 (1995) 177. [8] S.K. Noh, J. Kim, J. Jung, C.S. Ra, D. Lee, H.B. Lee, S.W. Lee, W.S. Huh, J. Organomet. Chem. 580 (1999) 90. [9] K.P. Reddy, J.L. Petersen, Organometallics 8 (1989) [10] H. Lang, S. Blau, A. Muth, K. Weiss, U. Neugebauer, J. Organomet. Chem. 490 (1995) C32. [11] I.E. Nifant ev, M.V. Borzov, A.V. Churakov, S.G. Mkoyan, L.O. Atovmyan, Organometallics 11 (1992) [12] W. Abriel, G. Baum, H. Burdorf, J. Heck, Z. Naturforsch. Teil. B 46 (1991) 841. [13] M. Bochmann, S.J. Lancaster, M.B. Hursthouse, M. Mazid, Organometallics 12 (1993) [14] (a) G.J.P. Britovsek, V.C. Gibson, D.F. Wass, Angew. Chem. 111 (1999) 448; (b) G.J.P. Britovsek, V.C. Gibson, D.F. Wass, Angew. Chem. Int. Ed. Engl. 38 (1999) 428. [15] H.G. Alt, J. Mol. Catal. A: Chem. 174 (2001) 35. [16] B. Peifer, W. Milius, H.G. Alt, J. Organomet. Chem. 553 (1998) 205. [17] H.G. Alt, M. Jung, J. Organomet. Chem. 580 (1999) 1. [18] J.L. Speier, Adv. Organomet. Chem. 17 (1979) 407. [19] U. Stehling, J. Diebold, R. Kirsten, W. Röll, H.H. Brintzinger, S. Jüngling, R. Mülhaupt, F. Langhauser, Organometallics 13 (1994) 964. [20] S.J. Palackal, Dissertation, Universität Bayreuth, [21] N. Klouras, H. Köpf, Monatsh. Chem. 112 (1981) 887. [22] C.S. Baygur, W.R. Tikkanen, J.L. Petersen, Inorg. Chem. 24 (1985) [23] K. Patsidis, H.G. Alt, W. Milius, S.J. Palackal, J. Organomet. Chem. 509 (1996) 63.

23 Festphasensynthese Theorie - Prinzip der Festphasensynthese - Schutzgruppenstrategien - Mechanismen Peptidkupplung und Nebenreaktionen - Vor- und Nachteile der Festphasensynthese Techniken - Schüttler - Zentrifugieren - Arbeiten in Spritzen mit Fritte - Arbeiten mit Aminosäuren Reagenzien und Lösungsmittel - Fmoc-Leu-Wang Harz - Fmoc-Tyr(tBu)-OH - Fmoc-Lys(Boc)-OH - Fmoc-Ile-OH - O-(Benzotriazol-1-yl)-N,N,N,N -tetramethyluroniumtetrafluoroborat (TBTU) - N,N-DImethylformamid (DMF) - Dichlormethan (DCM) - Diisopropylethylamin (DIPEA) - Trifluoressigsäure (TFA) - Triisopropylsilan (TIS) - Diethylether - Piperidin Vorschrift Ziel des Versuches ist die Darstellung der beiden Tetrapeptide H-Tyr-Ile-Lys-Leu-OH und H- Lys-Tyr-Lys-Leu-OH.

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