Hydrochlorination of Ruthenaphosphaalkenyls: Unexpectedly Facile Access to Alkylchlorohydrophosphane Complexes

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.