Crystal polarised spectra, and electronic structures, of some pseudotetrahedral cobalt(II) complexes with ‘soft’ bonding ligands

Abstract
The crystal polarised spectra of some pseudotetrahedral CoII complexes having chromophores [CoS2Cl2] and [CoP2X2](X = Br, I), have been recorded. The spectra may be assigned assuming an effective C2ν symmetry and spin–orbit coupling is found to be less important than the low-symmetry ligand field in modifying the electronic structure derived from Td symmetry. The sequence of components derived from Td symmetry is found to be: 4T1(F) : B1 < A2 < B2; 4T1(P) : B2 < A2 < B1. Crystal-field calculations fit the observed spectra only if parameters of the low symmetry components are treated as merely empirical parameters. Qualitative σ- and π-bonding parameters for the different donor ligands are derived and compared.

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