Stoichiometric Reaction Chemistry of Cationic Ruthenium Silylene Complexes toward Polar and Nonpolar Organic Substrates

Reactions of the cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(═SiRR′)][B(C6F5)4] (R = Mes, R′ = H, 1; R = R′ = Ph, 2) with alkenes, alkynes, ketones, and Lewis bases were explored. Addition of 1-hexene, 3,3-dimethylbut-1-ene, styrene, and cyclopentene to 1 afforded the disubstituted silylene products [Cp*(PiPr3)Ru(H)2(═SiMesR)][B(C6F5)4] (R = Hex, 3; R = CH2CH2tBu, 4; R = CH2CH2Ph, 5; R = C5H9, 6). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(═Si(CR═CHR′)Mes)][B(C6F)4] (R = R′ = Me, 7; R = H, R′ = tBu, 8). Complex 1 undergoes reactions with ketones to give the heteroatom-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(═Si(OCHPhR)Mes)][B(C6F)4] (R = Ph, 9; R = Me, 10). Interestingly, complexes 3–8 display a weak interaction between the hydride ligands and the silicon center, while 9 and 10 exhibit a relatively large interaction (as determined by 2JSiH values). The reaction of isocyanates with 1 resulted in the silyl complexes [Cp*(PiPr3)Ru(H)2(Si(Mes)[κ2-O(CH)(NC6H4R)][B(C6F5)4] (R = H, 11; R = CF3, 12), and an intermediate in this transformation is observed. Complex 2 was subjected to various Lewis bases to yield the base-stabilized silylene complexes [Cp*(PiPr3)Ru(H)2(SiPh2·L)][B(C6F)4] (L = DMAP, 13; L = Ph2CO, 14; L = PhCONH2, 15; L = NHMePh, 16, L = tBuSONH2, 18), and the reaction of 1 with NHMePh gave [Cp*(PiPr3)Ru(H)2(SiHMes·NHMePh)][B(C6F)4].