A1 Journal article (refereed)
Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems (2020)


Do, Dinh Cao Huan; Vasko, Petra; Fuentes, M. Ángeles; Hicks, Jamie; Aldridge, Simon (2020). Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems. Dalton Transactions, 49 (25), 8701-8709. DOI: 10.1039/D0DT01447H


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Publication details

All authors or editors: Do, Dinh Cao Huan; Vasko, Petra; Fuentes, M. Ángeles; Hicks, Jamie; Aldridge, Simon

Journal or series: Dalton Transactions

ISSN: 1477-9226

eISSN: 1477-9234

Publication year: 2020

Volume: 49

Issue number: 25

Pages range: 8701-8709

Publisher: Royal Society of Chemistry

Publication country: United Kingdom

Publication language: English

DOI: http://doi.org/10.1039/D0DT01447H

Open Access: Publication channel is not openly available

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/70405


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.



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Last updated on 2020-18-08 at 13:41