Chapter 46. Influence of the Steric Demand of Lithium Trialkylsilylamides, -Phosphanides and -Arsanides on the Metathesis Reaction with Tris(trimethylsilyl)methylzinc Chloride

  1. Prof. Norbert Auner2 and
  2. Prof. Johann Weis3
  1. Michael Wieneke and
  2. Matthias Westerhausen

Published Online: 28 APR 2008

DOI: 10.1002/9783527619917.ch46

Organosilicon Chemistry IV: From Molecules to Materials

Organosilicon Chemistry IV: From Molecules to Materials

How to Cite

Wieneke, M. and Westerhausen, M. (2000) Influence of the Steric Demand of Lithium Trialkylsilylamides, -Phosphanides and -Arsanides on the Metathesis Reaction with Tris(trimethylsilyl)methylzinc Chloride, in Organosilicon Chemistry IV: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619917.ch46

Editor Information

  1. 2

    Inst. für Anorganische Chemie, der Universität Frankfurt, Marie-Curie-Strasse 11, D-60439 Frankfurt am Main, Germany, Phone: 0 69/7 98-29180, -29591, Fax: 069/798-29188

  2. 3

    Wacker-Chemie GmbH, Geschäftsbereich S, Werk Burghausen, Johannes-Hess-Strasse 24, D-84489 Burghausen, Germany

Author Information

  1. Institut für Anorganische Chemie Ludwig-Maxirnilians-Universität Butenandtstr. 5–13, haus D, D41377 München, Germany Tel.: Int code +(89)2180 7481 — fax: Int code + (89)2180 7867

Publication History

  1. Published Online: 28 APR 2008
  2. Published Print: 17 JAN 2000

ISBN Information

Print ISBN: 9783527298549

Online ISBN: 9783527619917

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Keywords:

  • lithium;
  • metathesis reaction;
  • trialkylsilyl;
  • zinc

Summary

The reaction of lithium triisopropylsilylamide with (Me3Si)3CZnC1 yields tris(trimethylsilyl)methylzinc triisopropylsilylamide. The homologous phosphanide and arsanide give [(Me3Si)3CZn]2ESiiPr3 with E = P, As. Smaller substituents at the pentele atoms lead to the formation of zincates. Tetrakis(tetrahydrofuran-O)lithium bis[tris(trimethylsilyl)methylzinc] tris(anilide) is isolated from the metathesis reaction of lithium anilide and (MeCZnCl. The lithiation of Me3SiPH2 yields LiP(H)SiMe3; however, redistribution reactions lead also to LiPHz and LiP(SiMe3)z. The reaction of this mixture with (Me3Si)3CZnCI gives [(thf)4Li]'{[(Me3Si)3CZn], (p-Cl)(p3-PH)2).