Issue 25, 2020

Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems

Abstract

Electron-rich β-diketiminate ligands, featuring amino groups at the backbone β positions (“N-nacnac” ligands) have been employed in the synthesis of a range of silylene (SiII) complexes of the type (N-nacnac)SiX (where X = H, Cl, N(SiMe3)2, P(SiMe3)2 and Si(SiMe3)3). A combination of experimental and quantum chemical approaches reveals (i) that in all cases rearrangement to give an aza-butadienyl SiIV imide featuring a contracted five-membered heterocycle is thermodynamically favourable (and experimentally viable); (ii) that the kinetic lability of systems of the type (N-nacnac)SiX varies markedly as a function of X, such that compounds of this type can be isolated under ambient conditions for X = Cl and P(SiMe3)2, but not for X = H, N(SiMe3)2 and Si(SiMe3)3; and (iii) that the ring contraction process is most facile for systems bearing strongly electron-donating and sterically less encumbered X groups, since these allow most ready access to a transition state accessed via intramolecular nucleophilic attack by the SiII centre at the β-carbon position of the N-nacnac ligand backbone.

Graphical abstract: Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems

Supplementary files

Article information

Article type
Paper
Submitted
20 Apr 2020
Accepted
09 Jun 2020
First published
10 Jun 2020

Dalton Trans., 2020,49, 8701-8709

Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems

D. C. H. Do, P. Vasko, M. Á. Fuentes, J. Hicks and S. Aldridge, Dalton Trans., 2020, 49, 8701 DOI: 10.1039/D0DT01447H

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