Structures and Bond Energies of the Transition Metal Hexacarbonyls M(CO)6 (M = Cr, Mo, W). A Theoretical Study

Abstract

The geometries of the hexacarbonyls and pentacarbonyls of chromium, molybdenum, and tungsten are optimized at the Hartree-Fock and ML2 levels of theory using effective core potentials for the metal atoms. The M-CO bond lengths of Mo(CO) 6 and W(CO) 6 predicted at the ML2 level using moderate valence basis sets are in excellent agreement with experimental values. The Cr-CO bond length in Cr(CO) 6 calculated at ML2 is too short. The total bond energies of the metal hexacarbonyls calculated at the CCSD(T) level of theory are slightly lower than the experimentally derived values