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

Adam, Kenneth R., Anderson, Peter A., Astley, Timothy, Atkinson, Ian M., Charnock, John M., Garner, David C., Gulbis, Jacqueline M., Hambley, Trevor W., Hitchman, Michael A., Keene, F. Richard, and Tiekink, Edward R.T. (1997) 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. Dalton Transactions (4). pp. 519-530.

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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 formulation rather than as d⁷ cobalt(II)–ligand radical.

Item ID: 22744
Item Type: Article (Refereed Research - C1)
Keywords: visible-light irradiation; curved-wave theory; polypyridine complexes; homogeneous catalysis; carbon-dioxide; exafs calculations; crystal-structure; angular-overlap; water; reduction
ISSN: 1477-9234
Date Deposited: 10 Aug 2012 01:38
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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