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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 125, Issue 4, Pages 1079-1087Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja027857b
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A full understanding of the nature of excited states of transition metal complexes is important for understanding their chemical reactivity and role as intermediates in photochemically induced reactions. The ground and excited states of the [Pt-2(POP)(4)](4-) ion are investigated using density functional theory (DFT). Calculations with different functionals employing quasi-relativistic Pauli and ZORA formalisms all predict a Pt-Pt bond shortening and a slight Pt-P lengthening upon excitation to the lowest triplet state, the latter in apparent contradiction to experimental EXAFS results. The PW86LYP functional with the ZORA relativistic treatment is found to produce good agreement with time-resolved crystallographic and spectroscopic results. A topological bond path between the Pt atoms is found in both the ground and the excited states, though the electron localization function (ELF) indicates weak Pt-Pt covalent bonding for the excited state only. The spin density is mainly localized on the Pt atoms, giving insight into the ability of the triplet excited state to abstract hydrogen and halogen atoms from organic substrates.
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