Inorganic Chemistry, Vol.34, No.5, 1094-1099, 1995
Factors Affecting Chelation of Carboxylates to Cis-Diaqua Co(III) Complexes - Implications on the Reactivity of the Metal-Complexes for Hydrolyzing Esters, Amides, Nitriles, and Phosphates
The equilibrium constant for chelation of carboxylates to cis-diaqua tetraamine Co(III) complexes is highly sensitive to the tetraamine ligand structure, basicity of the chelating carboxylate, and solvent polarity. cis-Diaqua tetraamine Co(III) complexes that easily accommodate chelation of carboxylates are also highly reactive for hydrolyzing carboxyl esters, amides, nitriles, and phosphate esters. The X-ray crystal strcuture of [(trpn)Co(eta(2)-O2CC(CH3)(3)]-(ClO4)(2) has been determined : trpn = tris(3-aminopropyl)amine, C14H33N4O10Cl2CO, orthorhombic, P2(1)2(1)2(1), a = 8.7822(3)Angstrom, b = 14.9959(6)Angstrom, c = 17.5277(5)Angstrom, V = 2308.35(14) Angstrom(3), Z = 4.
Keywords:COBALT(III)-PROMOTED HYDROLYSIS;INTRAMOLECULAR ATTACK;PROMOTED HYDROLYSIS;ION;MECHANISM;HYDROXIDE;KINETICS;DIESTERS;CHLORIDE;WATER