Adocobinamide, the base-off analog of coenzyme 612 (adocobalamin). 2.1 probing the "base-on" effect in coenzyme B12 via cobalt-carbon bond thermolysis product and kinetic studies as a function of exogenous pyridine bases

Journal of the American Chemical Society

Volumn 118, Issue 45, 1996, Pages 11142-11154

  Garr, Cheryl D ^a   Sirovatka, Jeanne M ^a   Finke, Richard G ^b  

^a Department of Environmental and Radiological Health Sciences   (United States)

^b MDS Inc   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

COBALAMIN DERIVATIVE;

ARTICLE; HYDROLYSIS; REACTION ANALYSIS; TEMPERATURE;

EID: 0029959147     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja954110v     Document Type: Article

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72. +), the addition of TEMPO and Me2N-py was employed in this control experiment.
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75. Brown, K. L.; Evans, D. E. Inorg. Chem. 1994, 33, 6380. See also ref 33 therein in which Brown confirms the fact that the kinetic methods used in the present paper (and, indeed, those used for all our previous AdoCbl and related kinetic studies) do not suffer from the type of temperature measurement errors Brown and Evans describe (because of the completely different type of kinetic experiment and temperature control employed both in our previous work and herein).
76. 30c except for a slight shoulder at ca. 350 nm.
77. +-base starting material necessarily ensures that the Co-C thermal cleavage transition state of interest involves only the "natural" α-base complex,
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79. - and 2 H+, has never been unequivovcally characterized,
80. (b) There is also a reasonably facile "self-reduction" reaction of the corrin involving the c-side chain being converted to an internal corrin lactone or lactam (depending upon the pH), with concomitant reduction of the Comcobamide to the Co"cobamide; see ref 36 in an earlier paper120 as well as elsewhere32 for additional details.
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84. 28b)
85. (a) This control is still required, even though we have shown elsewhere"1 that the primary mode of binding is through the pyridine nitrogen and not the amine -MHz nitrogen,341" since there is always the possibility that a trace amount of the -NHi coordinated, base-on amine species could have a surprisingly high kinetic reactivity,
86. a = 5.2, Table 2). Note also that, at the higher, 110 °C thermolysis temperature, even less axial-base binding is expected due to the invariably negative AH for the axial-base binding equilibrium, (c) Brown and Brook performed a similar control in their recent publication, and they, too, found no evidence for the amine nitrogen binding.8
87. + Co-C bond thermolysis is directly related to the solvent viscosity, due to solvent-cage effects.28,33a
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90. assoc vs I/T plots are available as Supporting Information.
91. 1c
92. + form. We hope this brief explanation helps avoid future confusion over these points.
93. -, involvement in the present (unbuffered) solutions, established herein to be an accelerating factor of ca. 8 (Table 2, entry 3 vs entry 1). A second possible explanation is that different RCbi+-base conforme exist for Ado vs neopentyl or benzyl alkylcobamides as one proceeds along the productive Co-C homolysis reaction coordinate, and then, one must postulate in this hypothetical explanation that these conformers respond differently to increasingly electron-donating pyridine bases.
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96. 2).
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