Electrophilic and nucleophilic reactions of the vinylidene complex (Cp(PMe sub 3 ) sub 2 Ru double bond C double bond C(SMe) sub 2 )BF sub 4 and its derivatives

The cationic vinylidene complex (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(SMe){sub 2})BF{sub 4} (1) undergoes addition of electrophiles such as HBF{sub 4}{center dot}Et{sub 2}O, (MeSSMe{sub 2})SO{sub 3}CF{sub 3}, and (Me{sub 3}O)BF{sub 4} to give the complexes ((Ru) = Cp(PMe{sub 3}){sub 2}Ru) {l brace}Ru(S(Me)C{double bond}(H)SMe){r brace}(BF{sub 4}){sub 2} (2a), {l brace}Ru(S(Me)C{double bond}C(SMe)(H)){r brace}(BF{sub 4}){sub 2} (2b), {l brace}Ru(S(Me)C{double bond}C(H)SMe){sub 2}{r brace}(BF{sub 4}){sub 2} (3), and (Ru{double bond}C{double bond}C(SMe{sub 2})(SMe))(BF{sub 4}){sub 2} (4). An X-ray diffraction investigation shows that 2a crystallizes in space group C2/c with a = 31.558 (5) {angstrom}, b = 10.492 (2) {angstrom}, c = 16.484 (5) {angstrom}, {beta} = 100.89 (2){degree}, and Z = 8. The reaction of 4 with phosphines results in the cleavage of MeS{sup +} to form the sulfonio acetylide (Cp(PMe{sub 3}){sub 2}Ru-C{triple bond}CSMe{sub 2})BF{sub 4} (5) and (MeS-PPh{sub 2}R){sup +} (R = Me, Ph). Anionic nucleophiles such as NaSR (R = Et, Me) displace Me{sub 2}S from 4 to yield the vinylidene complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}(SR)(SMe))BF{sub 4} (R = Et (7), R = Me (1)). Complex 4 also reacts with pyridines, 4-NC{sub 5}H{sub 4}R (R = H, Et, NMe{sub 2} (DMAP)), and SEt{sub 2} to displace Me{sub 2}S to yield the dicationic vinylidene complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(4-NC{sub 5}H{sub 4}R)(SMe))(BF{sub 4}){sub 2} (R = H (8), Et (9), NMe{sub 2} (10)) and (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(SEt{sub 2})(SMe))(BF{sub 4}){sub 2} (11).