Reduction of the allylic substituents in Ni(I)(1,8-dipropenyl-1,4,8,11-tetraazacyclotetradecane)+ by the central Ni(I) in aqueous solutions.

The complex Ni(II)(1,8,-di-2-propenyl-1,4,8,11-tetraazacyclotetradecane)(2+), (NiL(1))(2+), was synthesized. X-ray crystallography demonstrates that the complex obtained is the trans-III isomer. The allylic substituents shift the redox couples (NiL(1))(3+/2+) and (NiL(1))(2+/+) anodically relative to the corresponding couples for Ni(II)(1,4,8,11-tetraazacyclotetradecane)(2+), (NiL(2))(2+), as expected. Surprisingly, the lifetime of (NiL(1))(+) in neutral aqueous solutions is shorter than that of (NiL(2))(+). Pulse radiolysis experiments reveal that the allylic substituents are reduced by the central Ni(I) ion. The first step in this reduction is a general acid catalyzed process. The results suggest that this step involves schematically the reaction Ni(I)[bond]NCH(2)CH[double bond]CH(2)(+) + H(+) --> Ni(III)[bond]NCH2CH2CH(2)(2+). The latter transient decomposes slowly with a half-life time of several minutes. Preliminary results support the suggestion that (NiL(2))(+), or other Ni(I)L complexes of this family, might reduce many alkenes present in the solution.