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Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems.
- Source :
-
Dalton Transactions: An International Journal of Inorganic Chemistry . 7/7/2020, Vol. 49 Issue 25, p8701-8709. 9p. - Publication Year :
- 2020
-
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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 49
- Issue :
- 25
- Database :
- Academic Search Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 144303544
- Full Text :
- https://doi.org/10.1039/d0dt01447h