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A"},{"key":"ja047915ob00036\/ja047915ob00036_1","unstructured":"The equation of the (lower) B3LYP line in Figure 1, BDE(Co\u2212C) = [\u2212122.2 (kcal\/mol) \u00c5-1][r(Co\u2212C)] + 267.50 kcal\/mol, can be compared with the correlation documented by Andruniow et al.21cfor a series of alkylcobalamin models:\u2009 BDE(Co\u2212C) = [\u2212168.3 (kcal\/mol) \u00c5-1][r(Co\u2212C)] + 355.88 kcal\/mol. The fact that the data for the vinylcobalamin (shown) and alkylcobalamin (not shown)21cmodels lie on different lines is likely due to the difference in hybridization at the carbon bound to cobalt. The calculations of Andruniow et al. in ref 21c were performed with the same combination of B3LYP and 6-31G(d)\/TZV basis sets, but the Co\u2212C BDE reported for methylcobalamin is without zero-point energy and thermochemical corrections, and is therefore greater than our value by ca. 5 kcal\/mol. Thus, to compare the results in ref 21c with those reported here, it is necessary to adjust the previousy-intercept by ca. 5 kcal\/mol given that all of the Co\u2212C BDEs in the previous work omit these corrections. The inclusion of these corrections would not be expected to significantly change the slope of the line."},{"key":"ja047915ob00037\/ja047915ob00037_1","first-page":"106","volume":"1","author":"The B","year":"1982","journal-title":"New York"},{"key":"ja047915ob00038\/ja047915ob00038_1","first-page":"282","volume":"102","author":"For DFT","year":"2002","journal-title":"Chem. Rev."},{"key":"ja047915ob00039\/ja047915ob00039_1","doi-asserted-by":"crossref","first-page":"5759","DOI":"10.1021\/ja00171a013","volume":"112","author":"Ervin K. M.","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"ja047915ob00041\/ja047915ob00041_1","first-page":"63","volume":"103","author":"Li J.","year":"1999","journal-title":"Theor. Chem. 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In aqueous solution, it is possible that water plays a role in this reaction as the initial nucleophile. Given thatK(H2O) for cob(II)alamin is 1.7 \u00d7 10-2,46this would make the calculated heterolysis free energies more endergonic by ca. 2.4 kcal\/mol."},{"key":"ja047915ob00063\/ja047915ob00063_1","doi-asserted-by":"crossref","first-page":"1466","DOI":"10.1002\/hlca.200390129","volume":"86","author":"Puchberger M.","year":"2003","journal-title":"Helv. Chim. Acta"},{"key":"ja047915ob00064\/ja047915ob00064_1","doi-asserted-by":"crossref","first-page":"425","DOI":"10.1016\/S0014-5793(97)00520-6","volume":"409","author":"Schumacher W.","year":"1997","journal-title":"FEBS Lett."},{"key":"ja047915ob00065\/ja047915ob00065_1","doi-asserted-by":"crossref","first-page":"426","DOI":"10.1007\/s00203-002-0409-3","volume":"177","author":"Neumann A.","year":"2002","journal-title":"Arch. 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