Complex OsH{κ-,,-[xant(PPr)]} () 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 OsH(SiR){κ-,,-[xant(PPr)]} [SiR = SiEt (), SiPh (), SiMe(OSiMe) ()] and H. 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(PPr)). This intermediate, which has been trapped to form OsH{κ-,-[xant(PPr)]}(PPr) (), 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 reacts with 1,1-diphenyl-2-propyn-1-ol and 1-phenyl-1-propyne. The reaction with the former affords Os{C≡CC(OH)Ph}{=C=CHC(OH)Ph}{κ-,,-[xant(PPr)]} (), which catalyzes the conversion of the propargylic alcohol into ()-2-(5,5-diphenylfuran-2()-ylidene)-1,1-diphenylethan-1-ol, via ()-enynediol. In methanol, the hydroxyvinylidene ligand of dehydrates to allenylidene, generating Os{C≡CC(OH)Ph}{=C=C=CPh}{κ-,,-[xant(PPr)]} (). The reaction of with 1-phenyl-1-propyne leads to OsH{κ-C,η-[CHCHCH=CH]}{κ-,,-[xant(PPr)]} () and PhCHCH=CH(SiEt).
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| http://dx.doi.org/10.1021/acs.organomet.2c00201 | DOI Listing |
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