Fourier transform ion cyclotron resonance mass spectrometry was used to characterize the gas-phase reactivity of Hf dipositive ions, Hf(2+)and HfO(2+), toward several oxidants: thermodynamically facile O-atom donor N(2)O, ineffective donor CO, and intermediate donors O(2), CO(2), NO, and CH(2)O. The Hf(2+) ion exhibited electron transfer with N(2)O, O(2), NO, and CH(2)O, reflecting the high ionization energy of Hf(+). The HfO(2+) ion was produced by O-atom transfer to Hf(2+) from N(2)O, O(2), and CO(2), and the HfO(2)(2+) ion by O-atom transfer to HfO(2+) from N(2)O; these reactions were fairly efficient. Density functional theory revealed the structure of HfO(2)(2+) as a peroxide. The HfO(2)(2+) ion reacted by electron transfer with N(2)O, CO(2), and CO to give HfO(2)(+). Estimates were made for the second ionization energies of Hf (14.5 ± 0.5 eV), HfO (14.3 ± 0.5 eV), and HfO(2) (16.2 ± 0.5 eV), and also for the bond dissociation energies, D[Hf(2+)-O] = 686 ± 69 kJ mol(-1) and D[OHf(2+)-O] = 186 ± 98 kJ mol(-1). The computed bond dissociation energies, 751 and 270 kJ mol(-1), respectively, are within these experimental ranges. Additionally, it was found that HfO(2)(2+) oxidized CO to CO(2) and is thus a catalyst in the oxidation of CO by N(2)O and that Hf(2+) activates methane to produce a carbene, HfCH(2)(2+).