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

作者信息

Kulkarni Naveen V, Das Animesh, Jayaratna Naleen B, Yousufuddin Muhammed, Dias H V Rasika

机构信息

Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019, United States.

出版信息

Inorg Chem. 2015 Jun 1;54(11):5151-3. doi: 10.1021/acs.inorgchem.5b00929. Epub 2015 May 18.

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(CN(t)Bu)3}(+) using CN(t)Bu as a trapping agent. {[HB(3,5-(CF3)2Pz)3]Zn(CN(t)Bu)3}(+) loses one zinc-bound CN(t)Bu easily to produce five-coordinate {[HB(3,5-(CF3)2Pz)3]Zn(CN(t)Bu)2}(+).