Syntheses of ketonated disulfide-bridged diruthenium complexes via C-H bond activation and C-S bond formation

The alpha-C-H bonds of 3-methyl-2-butanone, 3-pentanone, and 2-methyl-3-pentanone were activated on the sulfur center of the disulfide-bridged ruthenium dinuclear complex [(RuCl(P(OCH3)3)2)2(mu-S2)(mu-Cl)2] (1) in the presence of AgX (X = PF6, SbF6) with concomitant formation of C-S bonds to give the corresponding ketonated complexes [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SSCHR1COR2)(Ru(CH3CN)3(P(OCH3)3)2)]X3 ([5](PF6)3, R1 = H, R2 = CH(CH3)2, X = PF6; [6](PF6)3, R1 = CH3, R2 = CH2CH3, X = PF6; [7](SbF6)3, R1 = CH3, R2 = CH(CH3)2, X = SbF6). For unsymmetric ketones, the primary or the secondary carbon of the alpha-C-H bond, rather than the tertiary carbon, is preferentially bound to one of the two bridging sulfur atoms. The alpha-C-H bond of the cyclic ketone cyclohexanone was cleaved to give the complex [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SS-1- cyclohexanon-2-yl)(Ru(CH3CN)3(P(OCH3)3)2)](SbF6)3 ([8](SbF6)3). And the reactions of acetophenone and p-methoxyacetophenone, respectively, with the chloride-free complex [(Ru(CH3CN)3(P(OCH3)3)2)2(mu-S2)]4+ (3) gave [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SSCH2COAr)(Ru(CH3CN)3(P(OCH3)3)2)](CF3SO3)3 ([9](CF3SO3)3, Ar = Ph; [10](CF3SO3)3, Ar = p-CH3OC6H4). The relative reactivities of a primary and a secondary C-H bond were clearly observed in the reaction of butanone with complex 3, which gave a mixture of two complexes, i.e., [(Ru(CH3CN)2(P(OCH3)3)20(mu-SSCH2COCH2CH3)(Ru(CH3CN)3(P(OCH3)3)2)](CF3SO3)3 ([11](CF3SO3)3) and [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SSCHCH3COCH3)(Ru(CH3CN)3(P(OCH3)2)](CF3SO3)3 ([12](CF3SO3)3), in a molar ratio of 1:1.8. Complex 12 was converted to 11 at room temperature if the reaction time was prolonged. The relative reactivities of the alpha-C-H bonds of the ketones were deduced to be in the order 2 degrees > 1 degree > 3 degrees, on the basis of the consideration of contributions from both electronic and steric effects. Additionally, the C-S bonds in the ketonated complexes were found to be cleaved easily by protonation at room temperature. The mechanism for the formation of the ketonated disulfide-bridged ruthenium dinuclear complexes is as follows: initial coordination of the oxygen atom of the carbonyl group to the ruthenium center, followed by addition of an alpha-C-H bond to the disulfide bridging ligand, having S=S double-bond character, to form a C-S-S-H moiety, and finally completion of the reaction by deprotonation of the S-H bond.