A COMPARATIVE FULLY RELATIVISTIC NONRELATIVISTIC 1ST-PRINCIPLES X(ALPHA)-DVM AND PHOTOELECTRON SPECTROSCOPIC INVESTIGATION OF ELECTRONIC-STRUCTURE IN HOMOLOGOUS 4F AND 5F TRIS(ETA(5)-CYCLOPENTADIENYL)METAL(IV)ALKOXIDE COMPLEXES
A. Gulino et al., A COMPARATIVE FULLY RELATIVISTIC NONRELATIVISTIC 1ST-PRINCIPLES X(ALPHA)-DVM AND PHOTOELECTRON SPECTROSCOPIC INVESTIGATION OF ELECTRONIC-STRUCTURE IN HOMOLOGOUS 4F AND 5F TRIS(ETA(5)-CYCLOPENTADIENYL)METAL(IV)ALKOXIDE COMPLEXES, Inorganic chemistry, 32(18), 1993, pp. 3873-3879
The electronic structure of (eta5-C5H5)3MOR (M = Ce, Th, U) complexes
has been investigated by He I and He II UV photoelectron spectroscopy
combined with SCF Xalpha-DVM calculations. Fully relativistic Dirac-Sl
ater calculations were also carried out for the M = Th complex. The no
nrelativistic calculations indicate that metal-ligand interactions inv
olving the highest energy ligand orbitals involve primarily metal 5f o
rbitals while 6d admixtures are found for lower energy orbitals. The M
-0 bonding is both sigma and pi in nature and involves primarily metal
6d atomic orbitals. Evidence of a charge redistribution mechanism alo
ng the CH3 --> O --> M --> Cp3 direction provides a satisfactory expla
nation for the shortened M-0 distances and strong propensity for nearl
y linear M-O-CH3 linkages observed in diffraction studies. The fully r
elativistic calculations show that metal d contributions are slightly
underestimated at the nonrelativistic level. Such deviations do not, h
owever, alter the overall description of the metal-ligand bonding. The
nonrelativistic configuration of the metal center compares well with
the relativistic data. Gas-phase ionization energies can be accurately
and comparably evaluated at the computationally more efficient nonrel
ativistic level if optimized basis sets and potential representations
are used.