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 photogenerated CF3. radicals to both aryl and alkyl carbon atoms was also confirmed. The observed behaviour was rationalized by considering the electronic structure of the involved species, which all show ligand‐field inversion. Moreover, the homolytic pathway constitutes experimental evidence for the marked covalent character of the M−C bond. The relative stability of these M−C bonds was evaluated by energy‐resolved mass spectrometry (ERMS) and follows the order Cu
The homoleptic silver(I) compound [PPh ][CF AgCF ] (1) provides a convenient entry to the homoleptic silver(III) derivative [PPh ][Ag(CF ) ] (2). Once isolated as pure substances, these compounds exhibit marked thermal stabilities. Their structural and spectroscopic properties have been experimentally established. Moreover, their electronic structures have been calculated by theoretical methods. The electronic structure of the oxidized species [Ag(CF ) ] provides a new case of ligand-field inversion caused by the CF ligands.
Organosilver(III) fluoride complexes have been assigned a key role in different fluorination processes. To the best of our knowledge, however, none of them seem to have been isolated or even detected thus far. Here we report on the successful synthesis of the trifluoromethyl derivative [PPh4][(CF3)3AgF], which has been isolated in high yield. The thermodynamic stability of the Ag−F bond is shown by calculation and demonstrated by multistage mass spectrometry (MSn) under collision‐induced dissociation (CID) conditions. Nevertheless, the substantial elongation found in the Ag−F bond (X‐ray) is correlated with a marked nucleophilic character of the terminal F ligand. This Ag−F bond is, in fact, quite reactive: it suffers hydrolysis and is also solvolyzed by thiols.
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