Hydrochlorination of ruthenaphosphaalkenyls: unexpectedly facile access to alkylchlorohydrophosphane complexes

Greenacre, Victoria K, Day, Iain J and Crossley, Ian R (2017) Hydrochlorination of ruthenaphosphaalkenyls: unexpectedly facile access to alkylchlorohydrophosphane complexes. Organometallics, 36 (2). pp. 435-442. ISSN 0276-7333

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The novel ruthenaphosphaalkenyls [Ru{P═C(H)SiMe2R}Cl- (CO)(PPh3)2] (R = p-C6H4CF3, nBu) have been prepared for the first time, and studied alongside precedent analogues (R = Me, Ph, p-tol) for their reactions with HCl. In contrast to chemistry defined for the tert-butyl congener [Ru{P═C(H)tBu}Cl(CO)(PPh3)2], which initially adds a single equivalent of HCl across the Ru−P linkage, all five silyl derivatives undergo spontaneous addition of a second equivalent to afford [Ru{η1-PHCl−CH2SiMe2R}Cl(CO)(PPh3)2], extremely rare examples of coordinated “PHXR” type ligands. Where R = SiMe3, a distorted octahedral geometry with a conformationally restricted “PHXR” ligand is observed crystallographically; this structure is appreciably retained in solution, as determined from multinuclear NMR spectroscopic features, which include a Karplus-like PPh3−Ru−P−H spin−spin coupling dependence. Computational data suggest a silyl-induced increase in negative charge density at the phosphaalkenic carbon, rather than an intrinsic thermodynamic driver, as the likely origin of the disparate reactivity.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Depositing User: Ian Crossley
Date Deposited: 12 Jan 2017 12:50
Last Modified: 02 Jul 2019 16:50
URI: http://sro.sussex.ac.uk/id/eprint/66136

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Project NameSussex Project NumberFunderFunder Ref
Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wiresG1182ROYAL SOCIETYUF120021