Stopped-Flow Spectrophotometric Study of the Kinetics and Mechanism of CO(2) Uptake by cis-[Cr(C(2)O(4))(BaraNH(2))(OH(2))(2)](+) Cation and the Acid-Catalyzed Decomposition of cis-[Cr(C(2)O(4))(BaraNH(2))OCO(2)](−) Anion in Aqueous Solution

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-β-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.