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Sterically Encumbered Iridium Bis(N-heterocyclic carbene) Complexes: Air-Stable 14-Electron Cations and Facile Degenerate C–H Activation

Phillips, N., Rowles, J., Kelly, M.J., Riddlestone, Ian, Rees, N.H., Dervisi, A., Fallis, I.A. and Aldridge, S. (2012) Sterically Encumbered Iridium Bis(N-heterocyclic carbene) Complexes: Air-Stable 14-Electron Cations and Facile Degenerate C–H Activation Organometallics, 31 (23). pp. 8075-8078.

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Abstract

Cationic Ir(III) systems supported by a bis(expanded NHC) framework and featuring both agostic C–H and cis alkyl/hydride ligand sets have been targeted by protonation of the corresponding bis(alkyl) hydride complexes. Remarkably, the steric shielding afforded by the NHC substituents is such that these and related putative 14-electron cations are air and moisture stable. In solution, degenerate fluxional exchange is brought about by reversible σ-bond activation within the agostic alkyl C(sp3)–H bond; a non-dissociative mechanism is implied by the activation parameters ΔH⧧ = 8.8(0.4) kcal mol–1 and ΔS⧧ = −12.2(1.7) eu.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Phillips, N.
Rowles, J.
Kelly, M.J.
Riddlestone, Iani.riddlestone@surrey.ac.uk
Rees, N.H.
Dervisi, A.
Fallis, I.A.
Aldridge, S.
Date : 10 December 2012
Funders : Engineering and Physical Sciences Research Council (EPSRC)
DOI : 10.1021/om301060h
Depositing User : Clive Harris
Date Deposited : 24 Jun 2019 15:27
Last Modified : 24 Jun 2019 15:27
URI: http://epubs.surrey.ac.uk/id/eprint/852033

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