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The allcyne, MeSC-CSMe, initially displaces CI" in Cp(PMe3) 2RUCI at room temperature in MeOH to form a sulfurbound alkyne complex (Cp(PMe3)2Ru[S(Me)C-CSMe])PFg (1). Upon warming, 1 rearranges to the vinylidene complex [Cp(PMeg)2Ru=C=C(SMe)2]PFg (2). Complex 2 is reduced by Na[HBEt3] or Na/Hg to give the thioacetylide, Cp(PMe3)2RuC-C-SMe (5), and MeSSMe. The vinylidene complexes [Cp(PHe3)2Ru»C«C(R) (SMe) ]*** (6, R = H; 7, R • Me) are formed by electrophilic addition to the /9-carbon of the thioacetylide (5). Addition of CuCl to 5 forms Cp(PMe3) 2RU(CuCl) (C-C-SMe) (8) in which the copper is tr-bound through the C-C group. Reaction of 6 with methanol and ethanol yields the methoxycarbene complexes [Cp(PMe3)2Ru=C(OR)(CH2SMe)]BF4 (11a, R = Me; lib, R = Et). Deprotonation of 11a with NaOMe yields the vinyl complex Cp(PMe3)2Ru[C(0Me)=C(H)SMe] (12). Further addition of [Me30]BF4 to complexes 6 and 7 yields the first examples of sulfonium vinylidene dicationic complexes [Cp(PMe3)2Ru=C=C(R)(SMe2)](BF4)2 (9, R = H; 10, R = Me). An X-ray diffraction investigation shows that 9 crystallizes in space group P2i/n with a = 16.641 (2) Â, b = 8.861 (1) Â, c = 18.168 (2) A, = 114.80 (1)*, and Z = 4. Complexes 7 and 10 undergo one and two-electron reductions, respectively, to

The reactivity of the thioalkyne, MeSC[triple bond]CSMe, with ruthenium and tungsten complexes