Abstract
The organometal acetylides Cp(CO) 2MCCR ( 1, M Fe, R Ph and 2, M Ru, R Ph, t-Bu, Me) react with Co 2(CO) 8 to form the acetylide bridged trinuclear complexes Co 2(CO) 6-μ-[Cp(CO) 2MCCR] ( 3, M Fe, and 4, M Ru). Of these, the phenyl acetylide compounds undergo a non-destructive reaction with oxygen which results in the net loss of one carbon atom together with a CO ligand and the formation of the alkylidyne bridged clusters Co 2MCp(CO) 7(μ 3-CPh) ( 5, M Fe, and 6, M Ru). The molecular structure of 6 has been determined by an X-ray analysis. The mechanism of the oxidation reaction has been elucidated by 13C labelling of the acetylide α-C atom and EI mass spectrometry. It has been found that this C atom is converted to CO which, with a probability of 7/9, ends up as a CO ligand in the product cluster. This means that the oxidation converts the α-C to CO before elimination of the CO ligands.
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