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| - Microwave Spectra and Structures of KrAuF, KrAgF, andKrAgBr; 83Kr Nuclear Quadrupole Coupling and the Nature ofNoble Gas−Noble Metal Halide Bonding
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| - Microwave spectra of the complexes KrAuF and KrAgBr have been measured for the first timeusing a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laserablation of the metal from its solid and allowing the resulting plasma to react with an appropriate precursor(Kr, plus SF6 or Br2) contained in the backing gas of the jet (usually Ar). Rotational constants; geometries;centrifugal distortion constants; vibration frequencies; and 197Au, 79Br, and 81Br nuclear quadrupole couplingconstants have all been evaluated. The complexes are unusually rigid and have short Kr−Au and Kr−Agbonds. The 197Au nuclear quadrupole coupling constant differs radically from its value in an AuF monomer.In addition 83Kr hyperfine structure has been measured for KrAuF and the previously reported complexKrAgF. The geometry of the latter has been reevaluated. Large values for the 83Kr nuclear quadrupolecoupling constants have been found for both complexes. Both the 197Au and 83Kr hyperfine constants indicatea large reorganization of the electron distribution on complex formation. A thorough assessment of thenature of the noble gas−noble metal bonding in these and related complexes (NgMX; Ng is a noble gas,M is a noble metal, and X is a halogen) has been carried out. The bond lengths are compared with sumsof standard atomic and ionic radii. Ab initio calculations have produced dissociation energies along withMulliken populations and other data on the electron distributions in the complexes. The origins of the rigidity,dissociation energies, and nuclear quadrupole coupling constants are considered. It is concluded that thereis strong evidence for weak noble gas−noble metal chemical bonding in the complexes.
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