M−C Bond Homolysis in Coinage-Metal [M(CF3)4]− Derivatives
Correction(s) for this article
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Berichtigung: M−C Bond Homolysis in Coinage-Metal [M(CF3)4]− Derivatives
- Volume 132Issue 7Angewandte Chemie
- pages: 2563-2563
- First Published online: February 3, 2020
Dr. Miguel Baya
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorM. Sc. Daniel Joven-Sancho
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorProf. Dr. Pablo J. Alonso
Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorDr. Jesús Orduna
Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorCorresponding Author
Dr. Babil Menjón
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorDr. Miguel Baya
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorM. Sc. Daniel Joven-Sancho
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorProf. Dr. Pablo J. Alonso
Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorDr. Jesús Orduna
Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorCorresponding Author
Dr. Babil Menjón
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain
Search for more papers by this authorDedicated to Professor Pablo Espinet on the occasion of his 70th birthday
Abstract
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<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.
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