Synthesis and Characterization of Molybdenum Carbide Clusters Mon C4n (n equals 1 to 4)

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Laser radiation (XeCl laser, 308-nanometer wavelength) focused into a cell containing Mo(CO)6 vapor produced ultrafine particles in the extended waist of the laser beam. Negative ion mass spectrometry revealed molybdenum carbide cluster ions with a stoichiometry Mon C4n (n equals 1 to 4). The Mon C4nminus (n equals 2 to 4) ions are completely unreactive with NH3, H2 O, and O2, suggesting structures in which the molybdenum atoms are unavailable for coordination to additional ligands. Collision-induced dissociation studies of these anions show the loss of MoC4 units as the main fragmentation pathway. This observation, together with the lack of addition reactions, provides a basis for structures in which a planar cluster of two, three, or four molybdenum atoms is surrounded by, and bonded to, carbon dimers.

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