ABSTRACT
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 MonC4n (n = 1 to 4). The MonC4n(-) (n = 2 to 4) ions are completely unreactive with NH(3), H(2)O, and O(2), 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 MoC(4) 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.
ABSTRACT
Laser vaporization experiments with graphite in a supersonic cluster beam apparatus indicate that the smallest fullerene to form in substantial abundance is C(28). Although ab initio quantum chemical calculations predict that this cluster will favor a tetrahedral cage structure, it is electronically open shell. Further calculations reveal that C(28) in this structure should behave as a sort of hollow superatom with an effective valence of 4. This tetravalence should be exhibited toward chemical bonding both on the outside and on the inside of the cage. Thus, stable closed-shell derivatives of C(28) with large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps should be attainable either by reacting at the four tetrahedral vertices on the outside of the C(28) cage to make, for example, C(28)H(4), or by trapping a tetravalent atom inside the cage to make endothedral fullerenes such as Ti@C(28). An example of this second, inside route to C(28) stabilization is reported here: the laser and carbon-arc production of U@C(28).
