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- W2572199841 abstract "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 PPPh3–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." @default.
- W2572199841 created "2017-01-26" @default.
- W2572199841 creator A5055394832 @default.
- W2572199841 creator A5069459339 @default.
- W2572199841 creator A5074960150 @default.
- W2572199841 date "2017-01-11" @default.
- W2572199841 modified "2023-10-03" @default.
- W2572199841 title "Hydrochlorination of Ruthenaphosphaalkenyls: Unexpectedly Facile Access to Alkylchlorohydrophosphane Complexes" @default.
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- W2572199841 doi "https://doi.org/10.1021/acs.organomet.6b00829" @default.
- W2572199841 hasPublicationYear "2017" @default.
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