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A comparative study of the homoleptic [M(CF₃)₄]⁻ complexes of all three coinage metals (M = Cu, Ag, Au) reveals that homolytic M-C bond cleavage is favoured in every case upon excitation in the gas phase (CID-MS²). Homolysis also occurs in solution by photochemical excitation. Transfer of the photo-generated CF₃• radicals to both aryl and alkyl carbon atoms was also confirmed. The observed behaviour is rationalized attending to the electronic structure of the involved species, which all show ligand-field inversion. Moreover, the homolytic path gives experimental proof of the marked covalent character of the M-C bond. The relative stability of these M-C bonds has been evaluated by energy-resolved mass spectrometry (ERMS) and follows the order: Cu < Ag < Au. The qualitatively similar and rather uniform behaviour experimentally observed for all three coinage metals gives no ground to suggest variation in the metal oxidation state along the group.
This article was published in the following journal.
Name: Angewandte Chemie (International ed. in English)
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