Study of the electronic structure of M(CO)5Cl complexes (M = Mn, Re) using X-ray spectroscopy and density-functional theory
The electronic structure of M(CO)5Cl metal complexes (M = Mn, Re) has been investigated by X-ray emission spectroscopy. The obtained X-ray emission C Kα, OKα, Cl Kβ1, MnLα, and MnKβ5 spectra for Mn(CO)5Cl and ReLβ5 spectra for Re(CO)5Cl have been interpreted on the basis of the quantum-mechanical calculations by the method of density-functional theory, using the Gaussian-98 program. The investigation of Mn(CO)5Cl and Re(CO)5Cl showed similarity of the electronic structure of both complexes. Only small differences have been revealed in the energy structure and orbital occupancies of the atomic orbitals of the corresponding molecular orbitals; these differences are caused by the difference of the type of metal ions and the molecule geometry. On the basis of the performed quantum-mechanical calculations, theoretical X-ray emission spectra have been constructed, which reproduce well the characteristic features of the corresponding experimental spectra of M(CO)5Cl metal complexes (M = Mn, Re).