Zinc-Mediated Carbene Insertion to C–Cl Bonds of Chloromethanes and Isolable Zinc(II) Isocyanide Adducts

The zinc adduct {[HB­(3,5-(CF3)2Pz)3]­Zn}+, which was generated from [HB­(3,5-(CF3)2Pz)3]­ZnEt and [Ph3C]­{B­[3,5-(CF3)2C6H3]4}, catalyzes the activation of C–halogen bonds of chloromethanes via carbene insertion. Ethyl diazoacetate serves as the carbene precursor. The presence of {[HB­(3,5-(CF3)2Pz)3]­Zn}+ in the reaction mixture was confirmed by obtaining {[HB­(3,5-(CF3)2Pz)3]­Zn­(CNtBu)3}+ using CNtBu as a trapping agent. {[HB­(3,5-(CF3)2Pz)3]­Zn­(CNtBu)3}+ loses one zinc-bound CNtBu easily to produce five-coordinate {[HB­(3,5-(CF3)2Pz)3]­Zn­(CNtBu)2}+.