Structural distortion of the TpCo-L fragment (Tp = tris(pyrazolyl)borate). Analysis by X-ray diffraction and density functional theory
- Univ. of Delaware, Newark, DE (United States)
The crystal structures of coordinatively unsaturated [(Tp{sup NP}Co){sub 2}({mu}-N{sub 2})] and Tp{sup NP}Co(CO) show `bent` molecules, in which the fourth ligand (N{sub 2}, CO) is bent away from the pseudo-threefold axis of the TpCo-moiety by 27-38{degree}. Magnesium reduction of Tp{sup t-Bu,Me}Co(CO) yielded [Tp{sup t-Bu,Me}Co({mu}-CO)]{sub 2}Mg(THF){sub 4} which was also structurally characterized; the reduced carbonyl is `linear`. Extended Hueckel theory (EHT) and density functional theory (DFT) have been used to analyze the electronic structures and structural preferences of the TpCo-L fragment with L= CO(Co{sup I}, d{sup 8}), COLi(Co{sup 0}, d{sup 9}), and I(Co{sup II}, d{sup 7}). The actual and theoretical structure determinations were in good agreement. Based on these results we suggest that d{sup 8} TpCo-L complexes and, by analogy, isoelectronic CpM-L complexes assume `bent` structures. 47 refs., 10 figs., 5 tabs.
- OSTI ID:
- 232446
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 7 Vol. 118; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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