Abstract
The reaction of the Cr(xx)2(H2O)2 − (xx = oxalate, malonate and methylmalonate) complexes with dissolved CO2 was studied by stopped-flow spectrophotometry in the 7 < pH < 9 range and between 20 to 30°C at an ionic strength of 0.5 mol dm−3 (NaCl). Under the experimental conditions the aqua complex ion consists of a pH-dependent mixture of Cr(xx)2(H2O)2 −, Cr(xx)2(OH) (H2O)2− and Cr(xx)2(OH)2 3−. The monohydroxo and dihydroxo species undergo CO2 uptake and subsequent intramolecular carbonate ligand chelation independently, at rates which are readily distinguishable and are governed by the uptake rate constants k 1 and k 2 and chelation rate constants k 3 and k 4, respectively. Only the k 1 values for oxalato, malonato and methylmalonato complexes could be calculated; k 1 = 1084 and 1333 and 1650 mol−1 dm3 s−1, respectively. The results obtained were compared with those obtained from other systems that have either cobalt(III), iridium(III) or rhodium(III) as central atoms.
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Sai, C.S., Hela, P.G., Sridhar, Y. et al. Kinetic and mechanistic studies on the formation of bis(dicarboxylato)carbonatochromate(III) complexes. Transition Metal Chemistry 23, 249–252 (1998). https://doi.org/10.1023/A:1015788211974
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DOI: https://doi.org/10.1023/A:1015788211974