Reactions of Group 4 Metallocenes with Monosubstituted Acetonitriles: Keteniminate Formation versus C-C Coupling

被引：19

作者：

Becker, Lisanne ^{[1
]}

Haehnel, Martin ^{[2
]}

Spannenberg, Anke ^{[1
]}

Arndt, Perdita ^{[1
]}

Rosenthal, Uwe ^{[1
]}

机构：

[1] Univ Rostock, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany

[2] Univ Wurzburg, Inst Anorgan Chem, D-97974 Wurzburg, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 08期

关键词：

C-C coupling; deprotonation; H shift; metallacycles; metallocenes; 1,4-DIAZA-1,3-DIENE DAD COMPLEXES; NITRILE-NITRILE; TRIPLE-BOND; TO-N; REACTIVITY; CHEMISTRY; INSERTION; ZIRCONACYCLES; ACTIVATION; ZIRCONIUM;

D O I：

10.1002/chem.201406219

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactions of the Group 4 metallocene dichlorides [Cp-2'MCl2] (1a: M=Ti, Cp'=Cp*=eta(5)-pentamethylcyclopentadienyl, 1b: M=Zr, Cp'=Cp=eta(5)-cyclopentadienyl) with lithiated MesCH(2)-C N gave [Cp-2*TiCl(N=C=C(HMes))] (3; Mes=mesityl) in the case of 1a. For compound 1b, a nitrile-nitrile coupling resulted in a five-membered bridge in 4. The reaction of the metallocene alkyne complex [Cp-2*Zr(eta(2)-Me3SiC2SiMe3)] ( 2) with PhCH2-C N led in the first step to the unstable product [Cp-2*Zr(eta(2)-Me3SiC2SiMe3)(NC-CH2Ph)] (5). After the elimination of the alkyne, a mixture of products was formed. By variation of the solvent and the reaction temperature, three compounds were isolated: a diazadiene complex 6, a bis(keteniminate) complex 7, and 8 with a keteniminate ligand and a five-membered metallacycle. Subsequent variation of the Cp ligand and the metal center by using [Cp2Zr] and [Cp-2*Ti] with Me3SiC2SiMe3 in the reactions with PhCH2-C N gave complex mixtures.

引用

页码：3242 / 3248

页数：7

共 44 条

[11]

Brandenburg K, 2007, DIAMOND

[12] Facile synthesis of cyclopropene analogues of aluminum and an aluminum pinacolate, and the reactivity of LA1[η2-C2(SiMe3)2] toward unsaturated molecules (L = HC[(CMe)(NAr)]2, Ar=2,6-i-Pr2C6H3) [J].

Cui, CM ;

Köpke, S ;

Herbst-Irmer, R ;

Roesky, HW ;

Noltemeyer, M ;

Schmidt, HG ;

Wrackmeyer, B .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (37) :9091-9098

[13]

Diel BN, 1999, HETEROATOM CHEM, V10, P423, DOI 10.1002/(SICI)1098-1071(1999)10:5<423::AID-HC13>3.0.CO

[14]

2-B

[15] Magnesium(II) Complexes of the dpp-BIAN Radical-Anion: Synthesis, Molecular Structure, and Catalytic Activity in Lactide Polymerization [J].

Fedushkin, Igor L. ;

Morozov, Alexander G. ;

Chudakova, Valentina A. ;

Fukin, Georgy K. ;

Cherkasov, Vladimir K. .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (33) :4995-5003

[16] Migratory Insertion Reactions in Asymmetrical Guanidinate-Supported Zirconium Complexes [J].

Fernandez-Galan, Rafael ;

Antinolo, Antonio ;

Carrillo-Hermosilla, Fernando ;

Lopez-Solera, Isabel ;

Otero, Antonio ;

Serrano-Laguna, Amparo ;

Villasenor, Elena .

ORGANOMETALLICS, 2012, 31 (23) :8360-8369

[17] A comprehensive investigation of the chemistry and basicity of a parent amidoruthenium complex [J].

Fulton, JR ;

Sklenak, S ;

Bouwkamp, MW ;

Bergman, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (17) :4722-4737

[18] Methyl-substituted zirconocene-bis(trimethylsilyl)acetylene complexes (C(5)H(5-n)Me(n))(2)Zr(eta(2)-Me(3)SiC CSiMe(3)) (n=2-5) [J].

Hiller, J ;

Thewalt, U ;

Polasek, M ;

Petrusova, L ;

Varga, V ;

Sedmera, P ;

Mach, K .

ORGANOMETALLICS, 1996, 15 (17) :3752-3759

[19] Trimerization of phenylacetonitrile.: InMe3as a base for C-H acidic nitriles [J].

Iravani, E ;

Neumüller, B .

ORGANOMETALLICS, 2003, 22 (20) :4129-4135

[20] Decamethylsilicocene chemistry: Reaction with carbon-nitrogen triple-bond species [J].

Jutzi, P ;

Eikenberg, D ;

Neumann, B ;

Stammler, HG .

ORGANOMETALLICS, 1996, 15 (17) :3659-3663

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