Sterically encumbered iridium Bis(N-heterocyclic carbene) complexes: Air-stable 14-electron cations and facile degenerate C-H activation

Phillips, Nicholas, Rowles, Johnny, Kelly, Michael J., Riddlestone, Ian, Rees, Nicholas H., Dervisi, Athanasia ORCID: https://orcid.org/0000-0002-0590-5496, Fallis, Ian Andrew ORCID: https://orcid.org/0000-0001-7361-0182 and Aldridge, Simon 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. 10.1021/om301060h

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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
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Last Modified:	24 Oct 2022 10:29
URI:	https://orca.cardiff.ac.uk/id/eprint/44589

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