Equilibria and kinetics for pH-dependent axial ligation of bromomethyl(aquo)cobaloxime by aliphatic amine ligands

Journal of Chemical Sciences

M Bhoopal¹  N Ravi Kumar Reddy¹  S Satyanarayana1¹ 

[1] Department of Chemistry, Osmania University, Hyderabad 500 007, India$$

关键词: Alkylcobaloximes;    axial ligation;    bromomethyl(aquo)cobaloxime;    cycloamines.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

Kinetics and equilibria of axial ligation of bromomethyl(aquo) cobaloxime by a series of straight chain primary amines (methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine), cycloamines (cyclopentylamine, cyclohexylamine, cycloheptylamine) and secondary amines (N,N-dimethylamine, N,N-diethylamine) have been measured as functions of pH by spectrophotometric technique in aqueous solution, ionic strength 1 M (KCl) at 25°C. The rate of substitution of H2O varies with the 𝑝Ka of incoming ligand, thus establishing nucleophilic participation of the ligand in the transition state. Binding and kinetic data are interpreted based on the basicity and steric influence of the entering ligand. To compare the rate constants of the entering ligands, pH independent second-order rate constants (𝑘on) are calculated.

【 授权许可】

Unknown