Bond dissociation energies and structures of CuNO+ and Cu(NO)2+

The bond dissociation energies of CuNO+, Cu(NO)(2)(+), and CuAr+ are determined by means of guided ion beam mass spectrometry and quantum chemical calculations. From the experiment, the values D-0(Cu+-NO) = 1.13 +/- 0.05, D-0(ONCu+-NO) = 1.12 +/- 0.06, D-0(Cu+-Ar) = 0.50 +/- 0.07, and D-0(Cu+-Xe) = 1.02 +/- 0.06 eV are obtained. The computational approaches corroborate these results and provide additional structural data. The relative values of Do(Cu+-NO) and Do(Cu+-Xe) are consistent with the approximately thermoneutral formation of CuXe+ upon interacting CuNO+ with xenon. The sequential bond dissociation energies of Cu(NO)(2)(+) exhibit a trend similar to those of other Cu(I) complexes described in the literature. Although metathesis of nitric oxide to N-2 and O-2 is Of considerable interest, no evidence for N-N- or O-O-bond formations in Cu(NO)(n)(+) ions (with n up to 3) is obtained within the energy range studied experimentally.