Abstract
Abstract The rates of dissociation of bis-(N1-methylbiguanide)nickel(II) and bis-(N 1-phenylbiguanide)nickel(II) in aqueous acid have been studies by the stopped-flow spectrophotmetric technique. The reactions occur in two consecutive steps, the first being faster than the second, ultimately forming the aquometal ion and the protonated ligand. For each step the rate is acid dependent as expressed by kx=k1 x[H+], where kx is the observed rate constant. The results are consistent with a mechanism involving an assisted dissociative process involving the protonated complexes with considerable solvent participation in the transition state. The observed lability order is Ni(PhbigH)2+ 2 > Ni(MebigH)2+ 2 > Ni(BigH)2+ 2.
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