Molecular Complexes of Arenetricarbonylchromium, -molybdenum and -wolfram

概要

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Arenetricarbonylchromium forms a charge-transfer complex with 1,3,5-trinitrobenzene (1,3,5-TNB), while arenetricarbonylmolybdenum and -wolfram do not form a charge-transfer complex with 1,3,5-TNB. On the other hand, arenetricarbonylchromium, -molybdenum and -wolfram form a charge-transfer complex with tetracyanoethylene (TCNE). Since the intramolecular charge transfer from coordinated arene to carbonyls increases in the molybdenum and wolfram derivatives, 1,3,5-trinitrobenzene cannot form a molecular complex accepting an electronic charge of the coordinated arene. In the case of TCNE, however, a molecular complex is formed by an inner-sphere charge-transfer interaction between the acceptor and the central metal atom. Thus the stability of the TCNE molecular complexes is dependent upon the charge density of the central metal atom and also the steric effects due to the functional groups in coordinated arenes. The ionization potentials of the molybdenum and wolfram derivatives observed for their TCNE molecular complexes are almost equal but higher than those of the corresponding chromium derivatives, whereas the highest stability is obtained for the molybdenum derivatives.
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