Reductive Deprotonation and Dehydrogenation of Phenylhydrazine at a Nickel Center To Give a Nickel Diazenido Complex

The reaction of [LtBuNi­(OEt2)] (where LtBu = [HC­(CtBuNC6H3(iPr)2)2]−) with phenylhydrazine leads to the phenylhydrazido(1−) complex [LtBuNi­(η2-NPhNH2)] (1) with concomitant formation of H2. Treatment of 1 with potassium graphite in the presence of crown ether again leads to H2 evolution and affords the heterobimetallic complex [LtBuNi­(μ-η2:η2-NPhNH)]­K­(18-crown-6) containing the doubly deprotonated phenylhydrazido(2−) ligand. 1 can be converted into a phenyldiazenido complex [LtBuNi­(η1-NNPh)] in the course of a dehydrogenation reaction employing 1,2-diisopropylazo dicarboxylate (DIAD) as the oxidant.配合物[LtBuNi(二乙基醚合镍)]（其中LtBu代表阴离子配体[HC(C(叔丁基)NC₆H₃(异丙基)₂)₂]⁻）与苯肼发生反应，生成苯肼基(1−)配合物[LtBuNi(η²-NPhNH₂)]（标记为1），同时伴随氢气生成。将配合物1与石墨酸钾在冠醚存在下反应，同样会释放氢气，并得到异双核配合物[LtBuNi(μ-η²:η²-NPhNH)]K(18-冠-6)，该配合物含有双去质子化的苯肼基(2−)配体。在以偶氮二甲酸二异丙酯(1,2-二异丙基偶氮二甲酸酯, DIAD)作为氧化剂的脱氢反应中，配合物1可转化为苯基重氮基配合物[LtBuNi(η¹-NNPh)]。