Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silyleneElectronic supplementary information (ESI) available: Experimental description of catalysis, solution-phase and solid-state NMR spectra, and computational results. See DOI: 10.1039/c5dt02844b

An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ 3 -N,Si,C-PhB(Ox Me2 )(Ox Me2 SiHPh)Im Mes }Rh(H)CO][HB(C 6 F 5 ) 3 ] ( 2 , Ox Me2 = 4,4-dimethyl-2-oxazoline; Im Mes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox Me2 ) 2 Im Mes }RhH(SiH 2 Ph)CO ( 1 ) and B(C 6 F 5 ) 3 . The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox Me2 ) 2 Im Mes }RhH(SiHPh)CO][HB(C 6 F 5 ) 3 ] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C 6 F 5 ) 3 catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH 3 as the reducing agent. An oxazoline-stabilized rhodium silylene complex catalyzes the deoxygenation of carbonyls using PhSiH 3 as the reductant, including esters to ethers, amides to amines, and ketones to hydrocarbons rapidly at room temperature.