The electronic structures of a series of closely related U(η5-C5H5)3L (L = -CH3, -NH2, -BH4, -NCS) complexes has been studied using the SCF Hartree-Fock-Slater first-principles discrete variational Xα method in combination with He I and He II UV photoelectron spectroscopy. The theoretical results reproduce the experimental He I and He II photoelectron spectroscopic data, thus providing a reliable description of the metal-ligand bonding. Symmetry considerations render the 5f elements well-suited templates for coordination of the Cp3 ligand cluster. Interactions not restricted by symmetry appear partially or entirely modulated by the angular properties of π2-related MO's. Bonding interactions with ancillary L ligands involve either 5fz3 or 6dz2 metal orbitals, depending upon the energies of the unperturbed ligand orbital counterparts. Metal-ligand interactions cause the energies of 5f orbitals to split into a narrow manifold with a remarkable “ligand field” energy shift associated only with the 5fy(3x2-y2) orbital. The L→M charge donation results in an electronic configuration of the uranium atom which is almost constant throughout the U(C5H5)3L series and similar to that found in a fully relativistic SCF Dirac-Slater calculation on the simpler uranium atom. The stringent necessity of maintaining the uranium center in a particularly stable electronic configuration causes greater donation (hence larger covalency in the bonding) from ancillary L ligands to be compensated for by an increasing (L = -NH2 < -CH3 < -NCS < BH4−) ionic character of the U-Cp bonds. The present results show that nonrelativistic DV-Xα calculations, optimized for basis set and potential representation, reproduce experimental photoelectron spectroscopic data, including He I/He II relative intensity changes.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry