Co-C Bond Energies in Adenosylcobinamide and Methylcobinamide in the Gas Phase and in Silico.

Essential to biological activity of adenosylcobalamin (AdoCbl) and methylcobalamin (MeCbl) is the Co-C bond cleavage step. Hence, we report an accurate determination of the homolytic gas-phase Co-C bond dissociation energies in the related adenosyl- and methylcobinamides (41.5 ± 1.2 and 44.6 ± 0.8 k...

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Detalles Bibliográficos
Publicado en:	Journal of the American Chemical Society Vol. 135; no. 37; pp. 15648 - 15652
Autores principales:	Kobylianskii, Ilia J., Widner, Florian J., Kräutler, Bernhard, Chen, Peter
Formato:	Artículo
Publicado:	American Chemical Society 9/18/2013
Materias:	Chemical bonds Gas phase reactions Scission (Chemistry) Dissociation (Chemistry) Electronic structure Solvents Density functional theory
Acceso en línea:	Ver este registro en EBSCOhost

Descripción
Sumario:	Essential to biological activity of adenosylcobalamin (AdoCbl) and methylcobalamin (MeCbl) is the Co-C bond cleavage step. Hence, we report an accurate determination of the homolytic gas-phase Co-C bond dissociation energies in the related adenosyl- and methylcobinamides (41.5 ± 1.2 and 44.6 ± 0.8 kcal/mol, respectively) utilizing an energy-resolved threshold collision-induced dissociation technique. This approach allows for benchmarking of electronic structure methods separate from (often ill-defined) solvent effects. Adequacy of various density functional theory methods has been tested with respect to the experimentally obtained values.