C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru2S2 complexes.

Novel dicyanido-bridged dicationic Ru lll SSRu lll complexes [{Ru(P(OCH 3 ) 3 ) 2 } 2 (μ-S 2 )(μ-X) 2 {μ-m-C 6 H 4 (CH 2 CN) 2 }]-(CF 3 SΟ 3 ) 2 (4, X = Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH 3 ) 3 ) 2 } 2 -(μ.S 2 )(μ.X) 2 ] (1, X = Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C 4 S 2 ring-bridged complex [{Ru(P(OCH3)3) 2 } 2 {μ-SCH 2 C(CH3)=C(CH3)CH 2 S}(μ-X)2{μ-m-C 6 H 4 (CH2-CN) 2 }](CF 3 SO 3 ) 2 (6, X = Cl, Br). In addition, 4 reacted with 1-alkenes in CH 3 OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{μ-SS(CH2C=CHR)}(μ-Cl)2{μ-m-C 6 H 4 (CH2CN)2}](CF3S03) (7: R = CH 2 CH 3 , 9: R = CH 2- CH 2 CH 3 ) and alkenyl methyl disulfide complexes [{Ru(P(OCH3)3)2}2{μ-S(CH3)S(CH2C=HR)}(μ -Cl)2{μ-m-C 6 H 4 (CH2-CN) 2 }](CF 3 SO 3 ) 2 (8: R = CH 2 CH 3 , 10: R = CH 2 CH 2 CH 3 ) via the activation of an allylic C-H bond followed by the elimination of H + or condensation with CH 3 OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru-(P(OCH3)3)2}2{μ-SS(CH2C=CHCH20H)}(μ-Cl)2{μ-m-C6H4(CH2CN)2}](CF3S03) (11) via the elimination of H+ and [{Ru(P(OCH3)3)2}2(μ-SCH 2 CH=CHCH 2 S)(μ-Cl)2{μ-m-C 6 H 4 (CH2CN)2}](CF3S03)2 (12) via the intramolecular elimination of a H 2 O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.