Theoretical studies of organometallic compounds. 5. Alkyne and vinylidene complexes of molybdenum and tungsten in high-oxidation states.

Abstract

The geometries of the acetylene complexes MX 4 C 2 H 2 and the vinylidene isomers MX 4 CCH 2 (M=W, Mo; X=F, Cl) are theoretically predicted using quantum mechanical ab initio methods at the Hartree-Fock level of theory and relativistic effective core potentials for the transition metals. The optimized geometries and energies of the anionic complexes MX 5 C 2 H 2 - are also reported. The optimization of WX 5 C 2 H 2 - gives geometries for the chloro and fluoro complexes, which are in good agreement with experiment