Nickel complexes of a pincer NN2 ligand:: Multiple carbon-chloride activation of CH2Cl2 and CHCl3 leads to selective carbon-carbon bond formation

A new pincer-type bis(amino)amine (NN(2)) ligand and its lithium and nickel complexes, including Ni(II) methyl, ethyl, and phenyl complexes, were synthesized. The Ni(II) alkyl complexes react cleanly with alkyl halides. More interestingly, the Ni(II) alkyls undergo unprecedented reactions with CH(2)Cl(2) and CHCl(3) to cleave all the C-Cl bonds and replace them with C-C bonds. The reactions are highly selective and lead to the first efficient catalytic coupling of CHCl(2) with alkyl Grignards. A conversion of 82% and a turnover number of 47 are achieved within minutes. Coupling of CD(2)Cl(2) and 1,1-dichloro-3,3-dimethylbutane with (n)BuMgCl is also realized. Preliminary mechanistic study suggests a radical initiated process for these reactions.