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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 [CoL(2)](n+) species
journal contribution
posted on 2023-05-16, 10:53 authored by Adam, KR, Anderson, PA, Astley, T, Atkinson, IM, Charnock, JM, Garner, CD, Giulbis, JM, Hambley, TW, Hitchman, MA, Keene, FR, Tiekink, ERTThe nature of bonding in a series of complexes [CoL 2 ] 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 Co I -N ≈ Co II -N > Co III -N. Data from the various studies indicate that the 'cobalt(I)' state of the complex [Co{X(C 5 H 4 N-2) 3 } 2 ] + (X = CH or P) is better described by the d 8 cobalt(I)-ligand formulation rather than as d 7 cobalt(II)-ligand radical.
History
Publication title
Dalton TransactionsIssue
4Pagination
519-530ISSN
0300-9246Department/School
School of Natural SciencesPublisher
Royal Society of ChemistryPlace of publication
United KingdomRepository Status
- Restricted