309-11-5Relevant articles and documents
Mathey,Bensoam
, p. 3965,3967 (1971)
M?C Bond Homolysis in Coinage-Metal [M(CF3)4]? Derivatives
Baya, Miguel,Joven-Sancho, Daniel,Alonso, Pablo J.,Orduna, Jesús,Menjón, Babil
supporting information, p. 9954 - 9958 (2019/06/24)
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 CuAg?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.
CuI-Catalyzed Pentafluoroethylation of Aryl Iodides in the Presence of Tetrafluoroethylene and Cesium Fluoride: Determining the Route to the Key Pentafluoroethyl CuI Intermediate
Ohashi, Masato,Ishida, Naoyoshi,Ando, Kota,Hashimoto, Yu,Shigaki, Anna,Kikushima, Kotaro,Ogoshi, Sensuke
supporting information, p. 9794 - 9798 (2018/07/25)
The Cu(I)-catalyzed pentafluoroethylation of iodoarenes via the fluorocupration of tetrafluoroethylene (TFE) is disclosed. The active species, (phen)CuC2F5, was isolated and its molecular structure confirmed by a single-crystal X-ray diffraction analysis. The key to the successful suppression of the competing oligomerization of TFE is to refrain from stirring the reaction mixture. A mechanistic study clearly discarded the possibility that the catalytic reaction proceeds via a radical pathway.