Transition-Metal Complexes of Heavier Cyclopropenes: Non-Dewar-Chatt-Duncanson Coordination and Facile Si═Ge Functionalization.

Journal of the American Chemical Society
Paresh Kumar MajhiDavid Scheschkewitz

Abstract

Transition-metal complexes of cyclopropenes occur as fleeting intermediates of numerous metal-catalyzed organic transformations. A heavier analogue has now been obtained from the reaction of an NHC-stabilized silagermenylidene, bis(1,5-cyclooctadiene)nickel(0), and 1 equiv of N-heterocyclic carbene (NHC). The residual chloro functionality at the germanium end of the coordinated Ge═Si moiety of the thus formed 1H-disilagermirene is easily exchanged by treatment with anionic nucleophiles, which provides access to a series of differently substituted Si2Ge-cyclopropenes as nickel complexes in excellent yields. NMR spectroscopic data, X-ray crystallographic analysis, and DFT calculations indicate a coordination mode different from the metallacyclopropane and π-complex extremes of the Dewar-Chatt-Duncanson model: the σ-component of the Ge═Si double bond acts as donor and acceptor, leaving behind a nearly unsupported Si-Ge π-bond.

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Citations

Aug 13, 2021·Journal of the American Chemical Society·Paresh Kumar MajhiDavid Scheschkewitz
Oct 12, 2021·Chemical Communications : Chem Comm·Zhe WangManabu Abe

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