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Issue 19, 1998
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Mapping the unpaired electron density in [Pt(bipy)L2] (bipy = 2,2′-bipyridine; L = Cl, CN, 13CN): A combined EPR–ENDOR–theoretical study

Abstract

The X-band EPR and electron–nuclear double resonance (ENDOR) spectra of the formally , 17-electron radical anions [Pt(bipy)L2] (bipy = 2,2′-bipyridine; L = Cl, CN, 13CN) are reported. The 195Pt (I = 1/2, 34%) anisotropic hyperfine matrices are analysed in terms of both 5d and 6p contributions to the singly occupied molecular orbitals (SOMOs). For L = Cl there is 5.0% 5dyz and 7.6% 6pz character, for L = CNthere is <1% 5dyz and 13.1% 6pz. The bulk of the unpaired electron density is delocalised about the bipy π* system and ENDOR spectra reveal the superhyperfine couplings to the 1H, 14N and 13C (L = 13CN) nuclei. The unpaired electron densities in the 14N 2pz orbitals contributing to the π* systems are calculated to be 12% and 4% for L = Cl and CN, respectively. The cyanide π-orbitals make little contribution to the SOMO for [Pt(bipy)(CN)2]. There is a good agreement with density functional theory (DFT) MO calculations on the radical anions. DFT calculations also show the atomic orbital compositions of the lowest unoccupied (LU) MO of [Pt(bipy)L2] and the SOMO of [Pt(bipy)L2] to be virtually identical.

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Article type: Paper
DOI: 10.1039/A804498H
Citation: J. Chem. Soc., Faraday Trans., 1998,94, 2985-2991
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    Mapping the unpaired electron density in [Pt(bipy)L2] (bipy = 2,2′-bipyridine; L = Cl, CN, 13CN): A combined EPR–ENDOR–theoretical study

    E. J. L. McInnes, R. D. Farley, S. A. Macgregor, K. J. Taylor, L. J. Yellowlees and C. C. Rowlands, J. Chem. Soc., Faraday Trans., 1998, 94, 2985
    DOI: 10.1039/A804498H

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