Department of General and Inorganic Chemistry, University of Gdańsk, Sobieskiego 18/19, 80-952 Gdańsk, Poland.
Molecules. 2011 Sep 9;16(9):7746-61. doi: 10.3390/molecules16097746.
The kinetics of CO(2) uptake by the cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ complex cation and the acid hydrolysis of the cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- complex anion (where BaraNH(2) denotes methyl 3-amino-2,3-dideoxy-b-D-arabino-hexopyranoside) were studied using the stopped-flow technique. The reactions under study were investigated in aqueous solution in the 288-308 K temperature range. In the case of the reaction between CO(2) and cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ cation variable pH values (6.82-8.91) and the constant ionic strength of solution (H+, Na+, ClO(4)- = 1.0) were used. Carbon dioxide was generated by the reaction between sodium pyruvate and hydrogen peroxide. The acid hydrolysis of cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- was investigated for varying concentrations of H+ ions (0.01-2.7 M). The obtained results enabled the determination of the number of steps of the studied reactions. Based on the kinetic equations, rate constants were determined for each step. Finally, mechanisms for both reactions were proposed and discussed. Based on the obtained results it was concluded that the carboxylation (CO(2) uptake) reactions of cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+ and the decarboxylation (acid hydrolysis) of the cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]- are the opposite of each other.
使用停流技术研究了 cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+配合阳离子对 CO(2)的吸收动力学和 cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]-配合阴离子的酸水解反应(其中 BaraNH(2)表示甲基 3-氨基-2,3-二脱氧-β-D-阿拉伯己糖苷)。在 288-308 K 的温度范围内,在水溶液中研究了研究中的反应。在 CO(2)与 cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+阳离子之间的反应中,使用了可变 pH 值(6.82-8.91)和恒定的溶液离子强度(H+,Na+,ClO(4)-= 1.0)。二氧化碳是通过丙酮酸钠和过氧化氢之间的反应生成的。cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]-的酸水解反应是在不同浓度的 H+离子(0.01-2.7 M)下进行的。根据动力学方程,确定了每个步骤的速率常数。最后,提出并讨论了这两个反应的机制。根据获得的结果得出结论,cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)]+的羧化(CO(2)吸收)反应和 cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)]-的脱羧(酸水解)反应是相反的。