title: Co-C bond energies in adenosylcobinamide and methylcobinamide in the gas phase and in silico.
abstract: 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.
authors.affiliation: Laboratorium für Organische Chemie, ETH Zürich , 8093 Zürich, Switzerland.
authors.forename: Ilia J
authors.initials: IJ
authors.lastname: Kobylianskii
authors.forename: Florian J
authors.initials: FJ
authors.lastname: Widner
authors.forename: Bernhard
authors.initials: B
authors.lastname: Kräutler
authors.forename: Peter
authors.initials: P
authors.lastname: Chen
mesh_terms: D002244:Carbon / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D003038:Cobamides / Q000737:chemistry*; D005740:Gases; D008958:Models, Molecular; D015394:Molecular Structure; D044367:Phase Transition; D013816:Thermodynamics
chemical_list: D003038:Cobamides; D005740:Gases; C079634:adenosylcobinamide methyl phosphate; D003035:Cobalt; D002244:Carbon