Electronic and geometric structure of cationic and neutral chromium and molybdenum ammonia complexes

Abstract

High level quantum chemical approaches are used to study the geometric and electronic structures of M(NH3)n and M(NH3)n+ (M = Cr, Mo for n = 1-6). These complexes possess a dual shell electronic structure of the inner metal (3d or 4d) orbitals and the outer diffuse orbitals surrounding the periphery of the complex. Electronic excitations reveal these two shells to be virtually independent of the other. Molybdenum and chromium ammonia complexes are found to differ significantly in geometry with the former adopting an octahedral geometry and the latter a Jahn-Teller distorted octahedral structure where only the axial distortion is stable. The hexa-coordinated complexes and the tetra-coordinated complexes with two ammonia molecules in the second solvation shell are found to be energetically competitive. Electronic excitation energies and computed IR spectra are provided to allow the two isomers to be experimentally distinguished. This work is a component of an ongoing effort to study the periodic trends of transition metal solvated electron precursors.