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 = CN−there 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.