X-ray photoelectron spectroscopy and multiple scattering Xa calculations have been applied to a series of iridium halide complexes in order to corroborate the nature of the bondings inherent in this class of compounds. Our results seem to substantiate contentiously that higher oxidation states of indium favor the formation of covalent bonds. This conclusion is based on the observation that (1) successive bombardment of the iridium species by Ar ions almost definitely leads to a configuration in which indium is bound to at most one halide ion, and (2) the theoretical charge per ligand ion approaches systematically a value of {I -} in the limit as the formal oxidation state of indium approaches {l+}. The theoretical results are further authenticated by the fact that the experimental ionization energy of the Ir(4f) level in the different iridium halide complexes studied is seen to decrease as a result of exposure to Ar ions.

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Experimental results on the bombardment of some rhenium trihalides by argon ions in a photoelectron spectrometer have yielded lower-valency rhenium halides. The presence of the compounds have been made evident by the destabilization of the Re(4f) and the relative decrease in the halogen spectral line intensities. A theoretical approach to the energy of the Re(4f) states have been studied by the MS X-a method. The molecular model used in the calculations is made up of rhenium polyhalides in D, symmetry having the stn~cture R%X;-(n = 2,4,6). A discussion is also presented on the formation of multiple bonds as a result of the overlap between the d, orbitals of rhenium.

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