The complexes RuTp(PPh3)2Cl (1) and RuTp(PPh3)(py)Cl (2) catalyze the dimerization of HC⋮CR, where R = Ph, SiMe3, n-Bu, and t-Bu, to give 1,4- and 2,4-disubstituted butenynes with both conversion and selectivity strongly depending on the alkyne substituent, where the catalytic precursor is the neutral vinylidene complex RuTp(PPh3)(Cl)(=CCHR). The hydride complex RuTp(PPh3)2H (3) exhibits the same catalytic activity as 1 and 2.

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