55569-93-2Relevant articles and documents
Kinetics of substitution and redox reactions of the Rh2(OOCCH3)4+ complex with chloride and bromide ions
Cannon,Powell,Sarawek
, p. 1470 - 1474 (2008/10/08)
The title reactions were studied by the stopped-flow method. Rate constants k1X and k-1X for forward and reverse reactions Rh2(OAc)4+ + X- ? Rh2(OAc)4X at 5 and 25°C, I = 1.0 M (HClO4), are k1Cl = (2.3 ± 0.6) × 103 M-1 s-1 and (4.7 ± 1.6) × 103 M-1 s-1, k-1Cl = 14 ± 6 s-1 and 60 ± 14 s-1, k1Br = (6.8 ± 0.8) × 103 M-1 s-1 and (16.4 ± 0.5) × 103 M-1 s-1, and k-1Br = 6 ± 2 s-1 and 18 ± 3 s-1. Reduction of Rh2(OAc)4+ by Br- involves the equilibrium Rh2(OAc)4Br + Br- ? Rh2(OAc)4Br2- with K2Br = 150 M-1 (25°C). For the reaction Rh2(OAc)4Br2- → Rh2(OAc)4 + 1/2 Br2 + Br-, k = 600 s-1 (25°C). For the oxidation of Rh2(OAc)4 by Cl2, the rate expression is k[Rh2(OAc)4][Cl2], with k = 120 M-1 s-1 (25°C). The intermediate Rh2(OAc)4Br was detected by means of a rapid-scanning stopped-flow spectrophotometer.
