Photosubstitution kinetics and mechanism of Mo(IV) and W(IV) cyanide complexes with nitrogen heterocycle ligand- 1,3,5,7- tetraazatricyclodecane

Abstract

1164-1168Photochemical reaction of octacyano-molybdate (IV) and -tungstate (IV) with macrocyclic ligand- I ,3,5,7-tetraazatricyclodecane (hexamethylenetetramine or hexamine, urotropine) has been studied in aqueous medium.Molybdenum and tungsten cyanides form complexes with hexamine in I: I stoichiometry. The substitution of cyanide ligandby the macrocycle is confirmed by the observed shift in the transitions of the electronic spectra. However, the shift in thetransitions is significant in the tungsten than the molybdenum system. The rate of formation of the product depends on theconcentration of hydronium ions present in the solution