Cloke, Geoff, Green, JC and Jardine, CN (1999) Electronic structure and photoelectron spectra of bispentalene complexes of thorium and uranium. Organometallics, 18 (6). ISSN 02767333

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Abstract

The preparation of [U{¿8-C8H4(1,4-SiiPr 3)2}2] is reported. The binding of the pentalene ligand in an ¿8 mode is examined by density functional calculations and photoelectron spectroscopy. Geometry optimization of [M(¿8-C8H6)2], M = Th with D2d and D2 symmetry constraints, gives structures in good agreement with the X-ray structure found for [Th{¿8-C8H4(1,4-SiiPr 3)2}2); in particular the folded nature of the ligand is well reproduced by the calculation. Examination of the barrier to relative rotation of the two ligands only showed a significant energy rise when the two rings were eclipsed. Geometry optimization for M = U, assuming D2d symmetry and a triplet state, gave a structure similar to the Th compound but with shorter metal-carbon bond lengths. The two U f electrons were constrained to occupy degenerate orbitals of e symmetry. He I and He II spectra of [M{¿8-C8H4(1,4-SiiPr 3)2}2], M = Th and U, are presented and assigned with the aid of density functional calculations. The principal binding is by d bonds between the upper occupied p orbitals of the pentalene dianion and the actinide d and f orbitals of appropriate symmetry.

Item Type:	Article
Schools and Departments:	School of Life Sciences > Chemistry
Depositing User:	Geoff Cloke
Date Deposited:	06 Feb 2012 19:53
Last Modified:	06 Feb 2012 21:45
URI:	http://sro.sussex.ac.uk/id/eprint/22751

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