Kinetics of anation of cis-diaquo-bis-(1,3-diaminopropane) cobalt(iii) by oxalate

Dash, Anadi C. ; Nanda, Rabindra K. ; Ray, Nityananda (1982) Kinetics of anation of cis-diaquo-bis-(1,3-diaminopropane) cobalt(iii) by oxalate Journal of Coordination Chemistry, 12 (2). pp. 91-95. ISSN 0095-8972

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The kinetics of anation of cis-diaquobis(1,3-diaminopropane) cobalt(III) by oxalic acid and bioxalate anion have been studied at 35°, 40° and 45°C, I = 1.0 M(NaClO4). The observed rate law for the formation of Co(tmd)2C2O+4, - d in[Co(III)]T/dr = kobs = k1Q1[H2C2O4] + k2Q2[HC2O-4]/1 + Q1[H2C2O4] + Q2[HC2O-4], is valid in the range of [Ox]T = 0.03-0.50 M, pH=0.3-2.03. The anation rate constants, k1 and k2, for cis-{Co(tmd)2(OH2)3+2, H2C2O4) and cis-{Co(tmd)2(OH2)3+2, HC2O4-] ion pairs respectively are found to be virtually the same (k1 = 10.7 × 10-4 sec-1 and k2 = 11.0 ×10-4 sec-1 at 40°C). Temperature independent oxalic acid and bioxalate ion-pair association constants (Q1 and Q2) are 1.7(±0.3)M-1 and 11.5(±0.7)M-1, respectively. The activation enthalpy and entropy for k1 and k2 paths are 122.6 kJ mol-1 89.5 JK-1 mol-1 and 103.8 kJ mol-1, 29.3 JK-1 mol-1, respectively. The anation of cis-{Co(tmd)2(OH2)3+2, X} ion pairs (X = H2C2O4 or HC2O-4) is believed to involve Id mechanism. The reaction is catalysed by NO-3.

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