Silyl-Osmium(IV)-Trihydride Complexes Stabilized by a Pincer Ether-Diphosphine: Formation and Reactions with Alkynes

Complex OsH₄{κ³-P,O,P-[xant(PⁱPr₂)₂]} (1) activates the Si-H bond of triethylsilane, triphenylsilane, and 1,1,1,3,5,5,5-heptamethyltrisiloxane to give the silyl-osmium(IV)-trihydride derivatives OsH₃(SiR₃){κ³-P,O,P-[xant(PⁱPr₂)₂]} [SiR₃ = SiEt₃ (2), SiPh₃ (3), SiMe(OSiMe₃)₂ (4)] and H₂. The activation takes place via an unsaturated tetrahydride intermediate, resulting from the dissociation of the oxygen atom of the pincer ligand 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(PⁱPr₂)₂). This intermediate, which has been trapped to form OsH₄{κ²-P,P-[xant(PⁱPr₂)₂]}(PⁱPr₃) (5), coordinates the Si-H bond of the silanes to subsequently undergo a homolytic cleavage. Kinetics of the reaction along with the observed primary isotope effect demonstrates that the Si-H rupture is the rate-determining step of the activation. Complex 2 reacts with 1,1-diphenyl-2-propyn-1-ol and 1-phenyl-1-propyne. The reaction with the former affords Os{C≡CC(OH)Ph₂}₂{=C=CHC(OH)Ph₂}{κ³-P,O,P-[xant(PⁱPr₂)₂]} (6), which catalyzes the conversion of the propargylic alcohol into (E)-2-(5,5-diphenylfuran-2(5H)-ylidene)-1,1-diphenylethan-1-ol, via (Z)-enynediol. In methanol, the hydroxyvinylidene ligand of 6 dehydrates to allenylidene, generating Os{C≡CC(OH)Ph₂}₂{=C=C=CPh₂}{κ³-P,O,P-[xant(PⁱPr₂)₂]} (7). The reaction of 2 with 1-phenyl-1-propyne leads to OsH{κ¹-C,η²-[C₆H₄CH₂CH=CH₂]}{κ³-P,O,P-[xant(PⁱPr₂)₂]} (8) and PhCH₂CH=CH(SiEt₃).