Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(Ln)][BAr4F] (2a, Cp* = η3-C5Me5, Ln = N,N,N',N'-tetramethylethylenediamine, TMEDA; 2b, Ln = N,N,N',N'-tetraethylethylenediamine, TEEDA; 2c, Cp* = η1-C5Me5, Ln = N,N,N',N'',N''-pentamethyl-diethylenetriamine, PMDTA; Ar4F = (3,5-(CF3)2C6H3)4) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(Ln)ZnH(thf)m][BAr4F] (3a,b, m = 1; 3c, m = 0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis. Hydrogenolysis of the zinc cation 2b in the presence of benzophenone gave the zinc alkoxide [(TEEDA)Zn(OCHPh2)(thf)][BAr4F] (5b). Cation 2b was shown to catalytically hydrogenate N-benzylideneaniline. The PMDTA complex 2c underwent C-H bond activation in acetonitrile to give a dinuclear μ-κC,κN-cyanomethyl zinc complex [(PMDTA)Zn(CH2CN)]2[BAr4F]2 (6c).