Issue 11, 2013

Heavier carbene analogues and their derivatives as κ-El, κ2-El,N, and κ2-N,N′ ligands: different reactivity patterns for acyclic and cyclic diamidogermylenes and -stannylenes

Abstract

Because of the increasing importance of N-heterocyclic carbenes in organometallic chemistry we investigated the ligand properties of structurally-related acyclic and cyclic heavier carbene analogues with transition metal chlorides. Acyclic {(Me3Si)2N}2El, El = Ge and Sn, react with CuCl with transfer of one (Me3Si)2N ligand to yield the known copper tetramer {(Me3Si)2NCu}4. The cyclic Me2Si(μ-NtBu)2Ge, by contrast, binds copper through germanium only, furnishing a tetranuclear ladder structure with both terminal and bridging germylenes. The tin homologue, however, inserts into the CuCl bond, and the ensuing {Me2Si(μ-NtBu)2SnCl} ions then coordinate one copper ion via their tin atoms while sandwiching the remaining three copper ions in an unprecedented κ2-N,N′ fashion. Chemically-harder Cr(II)—created in a redox reaction of Me2Si(μ-NtBu)2Sn with CrCl3(THF)3—is not coordinated by tin, but chelated by both nitrogen atoms of one {Me2Si(μ-NtBu)2SnCl} ion and more weakly through the tin-bound chloride.

Graphical abstract: Heavier carbene analogues and their derivatives as κ-El, κ2-El,N, and κ2-N,N′ ligands: different reactivity patterns for acyclic and cyclic diamidogermylenes and -stannylenes

Supplementary files

Article information

Article type
Paper
Submitted
13 Oct 2012
Accepted
20 Dec 2012
First published
10 Jan 2013

Dalton Trans., 2013,42, 3835-3842

Heavier carbene analogues and their derivatives as κ-El, κ2-El,N, and κ2-N,Nligands: different reactivity patterns for acyclic and cyclic diamidogermylenes and -stannylenes

J. K. West, G. L. Fondong, B. C. Noll and L. Stahl, Dalton Trans., 2013, 42, 3835 DOI: 10.1039/C2DT32443A

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