An investigation of the electronic structure of some tris([eta][sup 5]-cyclopentadienyl)thorium(IV) and -uranium(IV) complexes by relativistic effective core potential ab initio calculations and gas-phase UV photoelectron spectroscopy

Journal Article · Thu Nov 11 04:00:00 EST 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100147a020· OSTI ID:5525231

Di Bella, S; Gulino, A; Lanza, G; Fragala, I L ^[1]; Marks, T J ^[2]

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1. Universita di Catania (Italy)
2. Northwestern Univ., Evanston, IL (United States)

Comparative relativistic effective core potential ab initio calculations for both Th(IV) and U(IV) Cp[sub 3]AnL (Cp = [eta][sup 5]-C[sub 5]H[sub 5]; L = CH[sub 3], BH[sub 4]) complexes are reported. The Cp-An bonding appears to be dominated by metal 6d orbitals interacting with ligand [pi][sub 2] orbitals. Metal 5f orbitals provide a smaller contribution but are crucial for stabilization of the Cp[sub 3]An cluster. The stability of the An-CH[sub 3] bonding depends upon interactions involving metal 6d[sub g(2)]-based orbitals directed along the An-CH[sub 3] vector. The L BH[sub 4] ligand interactions are mediated by d[sub xz] and d[sub yz] atomic orbitals, which are even better suited for favorable overlap and, hence, for greater metal-ligand [pi] covalency. Ground [sup 3]A[sub 2] states have been found to be the most stable for the U(IV) complexes. The experimental He I/He II photoelectron data are consistent with the quantum chemical calculations and indicate a close similarity between ground-state properties of the present Th(IV) and U(IV) complexes. 26 refs., 2 figs., 4 tabs.

• OSTI ID: 5525231
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:45; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400102 -- Chemical & Spectral Procedures
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
ACTINIDE COMPLEXES
CALCULATION METHODS
COMPLEXES
DATA
EIGENVALUES
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
HARTREE-FOCK METHOD
INFORMATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
SPECTROSCOPY
THEORETICAL DATA
THORIUM COMPLEXES
URANIUM COMPLEXES