Inorganic Chemistry, Vol.51, No.18, 9740-9747, 2012
Reductive Deprotonation and Dehydrogenation of Phenylhydrazine at a Nickel Center To Give a Nickel Diazenido Complex
The reaction of [(LNi)-Ni-tBu(OEt2)] (where L-tBu = [HC((CNC6H3)-N-tBu(Pr-i(2))(2)](-)) with phenylhydrazine leads to the phenylhydrazido(1-) complex [(LNi)-Ni-tBu(eta(2)-NPhNH2)] (1) with concomitant formation of H-2. Treatment of 1 with potassium graphite in the presence of crown ether again leads to H-2 evolution and affords the heterobimetallic complex [(LNi)-Ni-tBu(mu-eta(2):eta(2)-NPhNH))K(18-crown-6) containing the doubly deprotonated phenylhydrazido(2-) ligand. 1 can be converted into a phenyldiazenido complex [(LNi)-Ni-tBu(eta(1)-NNPh)] in the course of a dehydrogenation reaction employing 1,2-diisopropylazo dicarboxylate (DIAD) as the oxidant.