ACTIVATION PARAMETERS FOR THE REACTION OF AQUOCOBALAMIN (VITAMIN-B12A) WITH SMALL ANIONIC AND NEUTRAL LIGANDS

被引:31
作者
MARQUES, HM
机构
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1991年 / 02期
关键词
D O I
10.1039/dt9910000339
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
From the temperature dependence of the rate constants, activation enthalpies and entropies were determined for the reaction of aquocobalamin (vitamin B12a) with SCN-, S2O3(2-), NO2-, SO3(2-) and HSO3 -(ionic strength, l = 1.0 mol dm-3, KCl). These, and previously determined activation parameters for CN-, HCN, N3- and HN3, demonstrate the very small differences that exist between most small anionic and neutral ligands in their reactions with B12a. Exceptions are CN- and SO3(2-) which have, respectively, anomalously small and large values for DELTA H double-ended-dagger and DELTA S double-ended-dagger. These effects are possibly due to nucleophilic participation of these ligands in the transition state of the reaction.
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页码:339 / 341
页数:3
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共 23 条
[1]  
Betterton E.A., 1982, THESIS U WITWATERSRA
[2]   HETERONUCLEAR NMR-STUDIES OF COBALAMINS .7. PROTONATION OF THE CORRIN RING IN SULFURIC-ACID WATER MIXTURES [J].
BROWN, KL ;
PECK, S .
INORGANIC CHEMISTRY, 1987, 26 (25) :4143-4145
[3]   KINETICS OF REACTION OF CERTAIN VITAMIN-B12 ANALOGS WITH CYANIDE ION [J].
CONN, JB ;
WARTMAN, TG .
SCIENCE, 1952, 115 (2977) :72-73
[4]   TRANS EFFECT IN OCTAHEDRAL COMPLEXES .4. KINETIC TRANS EFFECT INDUCED BY THE S-BONDED THIOSULFATO LIGAND IN BIS(ETHYLENEDIAMINE)COBALT(III) COMPLEXES [J].
COOPER, JN ;
MCCOY, JD ;
KATZ, MG ;
DEUTSCH, E .
INORGANIC CHEMISTRY, 1980, 19 (08) :2265-2271
[5]  
De Tacconi N., 1979, J AM CHEM SOC, V101, P467, DOI [10.1021/ja00496a034, DOI 10.1021/JA00496A034]
[6]   CHEMISTRY OF VITAMIN B12 .9. EVIDENCE FOR 5-CO-ORDINATE COBALT(3) COMPLEXES [J].
FIRTH, RA ;
HILL, HAO ;
MANN, BE ;
PRATT, JM ;
THORP, RG ;
WILLIAMS, RJP .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1968, (10) :2419-+
[7]   CHEMISTRY OF VITAMIN B12 .11. SOME FURTHER FORMATION CONSTANTS [J].
FIRTH, RA ;
HILL, HAO ;
PRATT, JM ;
THORP, RG ;
WILLIAMS, RJP .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1969, (03) :381-+
[8]   STEREOCHEMISTRY AND REACTION-RATES OF ANIONOPENTAAMINE COMPLEXES OF COBALT(III) AND CHROMIUM(III) [J].
HOUSE, DA .
COORDINATION CHEMISTRY REVIEWS, 1977, 23 (03) :223-322
[9]   NUCLEOPHILIC PARTICIPATION OF INCOMING LIGANDS IN THE TRANSITION-STATE OF SUBSTITUTION-REACTIONS OF AQUOCOBALAMIN - KINETICS OF THE REACTION WITH IMIDAZOLE AND ITS DERIVATIVES [J].
MARQUES, HM ;
EGAN, TJ ;
MARSH, JH ;
MELLOR, JR ;
MUNRO, OQ .
INORGANICA CHIMICA ACTA, 1989, 166 (02) :249-255
[10]   THE COORDINATION OF IMIDAZOLE AND ITS DERIVATIVES BY AQUOCOBALAMIN [J].
MARQUES, HM ;
MARSH, JH ;
MELLOR, JR ;
MUNRO, OQ .
INORGANICA CHIMICA ACTA, 1990, 170 (02) :259-269