Journal article

Stabilization of cobalt(I) by the tripodal ligands tris(2-pyridyl)methane and tris(2-pyridyl)phosphine. Structural, spectroscopic and ab initio studies of the [CoL2]n species

KR Adam, PA Anderson, T Astley, IM Atkinson, JM Charnock, CD Garner, JM Gulbis, TW Hambley, MA Hitchman, FR Keene, ERT Tiekink

Journal of the Chemical Society - Dalton Transactions | Published : 1997

Abstract

The nature of bonding in a series of complexes [CoL2]n+ [L = the tripodal ligand tris(2-pyridyl)methane or tris(2-pyridyl)phosphine, n = 1-3] has been investigated by single-crystal X-ray diffraction, X-ray absorption and electronic spectroscopy and density functional theory ab initio calculations. The structural studies reveal that the cobalt ions each exist in a distorted octahedral geometry defined by six N-donor atoms; the cations are all centrosymmetric. In both series of complexes the bond lengths CoI-N ≈ CoII-N > CoIII-N. Data from the various studies indicate that the 'cobalt(I)' state of the complex [Co{X(C5H4N-2)3}2]+ (X = CH or P) is better described by the d8 cobalt(I)-ligand for..

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