A study of the molecular and electronic structures of the indium(i) phospholyls [InOf-PBuS] and [InOf-PaCaBu'j] by X-ray diffraction, photoelectron spectroscopy and density functional theory t

Clentsmith, Guy K B, Cloke, F Geoffrey N, Francis, Matthew D, Green, Jennifer C, Hitchcock, Peter B, Nixon, John F, Suter, James L and Vickers, David M (2000) A study of the molecular and electronic structures of the indium(i) phospholyls [InOf-PBuS] and [InOf-PaCaBu'j] by X-ray diffraction, photoelectron spectroscopy and density functional theory t. Journal of the Chemical Society, Dalton Transactions (11). pp. 1715-1721. ISSN 1470479X

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Abstract

The crystal and molecular structures of [In(r|5-P2C3But3)] are reported. He I and He II photoelectron (PE) spectra of [InCn'-PjQBu'i)] and of [In(n5-PjC3Bu'j)] are assigned by comparison with related systems and with the aid of density functional calculations of the ionisation energies (IE). In both cases the first PE band comprises ionisation from the ring n levels together with an ionisation from a Pa orbital. The second band is due to ionisation from an In-ring antibonding orbital with In s character. Other Per ionisation bands lie at higher IE. Substitution of CBu' by P within the five membered aromatic ring increases the IE of related bands. Geometry optimisation of the parent complexes [In(n5-P3C2H2)] and [In(n5-P2C3H3)] gave structural parameters in good agreement with the X-ray data. Attempts to find an energy minimum corresponding to n'-coordination were unsuccessful, the structures reverting to the n5-coordination mode. Bonding of the ring is principally due to overlap of the two upper occupied n orbitals with the In 5p orbitals. Some rehybridisation at the P atoms assists this overlap. Mulliken population analysis shows the In 5p occupation to be ca. half an electron in both cases.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Geoff Cloke
Date Deposited: 06 Feb 2012 20:48
Last Modified: 28 Mar 2012 13:21
URI: http://sro.sussex.ac.uk/id/eprint/28223
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