Kinetics of base hydrolysis of the cis-dichloro(1,4,7,10-tetra-azacyclododecane)rhodium(III) and cis-dichloro(1,4,8,11-tetra-azacyclotetradecane)rhodium(III) cations

Abstract

The kinetics of base hydrolysis of the two title cations, cis-[RhCl₂(cyclen)]⁺(cyclen = 1,4.7,10-tetra-azacyclo-dodecane) and cis-[RhCl₂(cyclam)]⁺(cyclam = 1,4,8,11-tetra-azacyclotetradecane), have been studied over a range of temperature at I= 0.1 mol dm^–3(KCl or K[NO₃]). The activation parameters have been obtained and possible mechanisms considered. The base-hydrolysis rate of cis-[RhCl₂(cyclen)]⁺, k_OH= 37 dm³ mol^–1 s^–1 at 25 °C and I= 0.1 mol dm^–3, is the highest yet reported for halogenorhodium(III) complexes of the [RhCl₂(N₄)]⁺ type.