The cationic zinc adduct {[HB (3,5-(CF3)(2)Pz)(3)]Zn(NCMe)(2)}ClO4 catalyzes the functionalizalion of tertiary, secondary, and primary C-H bonds of alkanes via carbene insertion. Ethyl diazoacetate serves as the :CHCO2Et carbene precursor. The counteranion, supporting ligand, and coordinating solvents affect the catalytic activity. An in situ generated {[HB (3,5-(CF3)(2)Pz)(3)]Zn}(+) species containing a bulkier {B[3,5-(CF3)(2)C6H3](4)}(-) anion gives the best results among the zinc catalysts used.