Photochemistry of the H2O/CO System Revisited: The HXeOH···CO Complex in a Xenon Matrix.

We report on the complex of a noble-gas hydride HXeOH with carbon monoxide. This species is prepared via the annealing-induced H + Xe + OH···CO reaction in a xenon matrix, the OH···CO complexes being produced by VUV photolysis of the H2O···CO complexes. The H-Xe stretching mode of the HXeOH···CO complex absorbs at 1590.3 cm-1 and it is blue-shifted by 12.7 cm-1 from the H-Xe stretching band of HXeOH monomer. The observed blue shift indicates the stabilization of the H-Xe bond upon complexation, which is characteristic of complexes of noble-gas hydrides. The HXeOH···CO species is the first complex of a noble-gas hydride with carbon monoxide and the second observed complex of HXeOH. On the basis of the MP2/aug-cc-pVTZ-PP calculations, the experimental complex is assigned to the structure, where the carbon atom of CO interacts with the oxygen atom of HXeOH.