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Hydrochlorination of ruthenaphosphaalkenyls: unexpectedly facile access to alkylchlorohydrophosphane complexes

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posted on 2023-06-09, 04:39 authored by Victoria K Greenacre, Iain Day, Ian CrossleyIan Crossley
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{?1-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.

Funding

Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wires; G1182; ROYAL SOCIETY; UF120021

History

Publication status

  • Published

File Version

  • Accepted version

Journal

Organometallics

ISSN

0276-7333

Publisher

American Chemical Society

Issue

2

Volume

36

Page range

435-442

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2017-01-12

First Open Access (FOA) Date

2018-01-12

First Compliant Deposit (FCD) Date

2017-01-12

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