The profound influence of a single metal-carbon bond on the reactivity of bio-relevant cobalt(III) complexes

Dalton Transactions : an International Journal of Inorganic Chemistry
Mohamed S A Hamza, R van Eldik

Abstract

This Perspective reports the development of mechanistic insight over the past 6 years, on the substitution behaviour of cobalamins that contain a single Co-C bond. The effect of the alkyl group, located in the trans position, on the thermodynamic, kinetic and ground state trans effect, was studied in detail. The substitution reactions of different alkylcobalamins with CN- were investigated, the apparent mechanistic discrepancy reported for the co-enzyme B12 was resolved and a logical explanation could be offered. In addition, a complete picture of the effect of pressure on the UV-Vis spectra of different base-on and base-off cobalamins is presented, which clearly shows the role of the alkyl group in controlling the equilibrium between five- and six-coordinate species, and the possible participation of such species in the studied ligand substitution reactions. The kinetics of the base-on/base-off equilibration was studied for the first time using a pH-jump technique. All in all the novel mechanistic information adds to the understanding of the profound effect that a single metal-carbon bond can have on the reactivity of such Co(III) complexes.

References

May 1, 1967·Biochemistry·W C Randall, R A Alberty
Feb 24, 2001·Inorganic Chemistry·M S HamzaR van Eldik
Oct 2, 2001·Inorganic Chemistry·M S HamzaR van Eldik
Jul 16, 1997·Inorganic Chemistry·Nicola E. BraschRudi van Eldik
Oct 24, 2001·Inorganic Chemistry·Trixie WagnerHarry P. C. Hogenkamp
Feb 19, 2002·Chemical Reviews·A. DrljacaW. J. le Noble

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Citations

Apr 22, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Ruibing WangDonal H Macartney

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