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Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives
Author(s) -
MoralesCerrada Roberto,
Fliedel Christophe,
Daran JeanClaude,
Gayet Florence,
Ladmiral Vincent,
Améduri Bruno,
Poli Rinaldo
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804007
Subject(s) - homolysis , chemistry , decarbonylation , bond cleavage , radical , photochemistry , bond dissociation energy , dissociation (chemistry) , crystallography , organic chemistry , catalysis
Thermal decarbonylation of the acyl compounds [Mn(CO) 5 (COR F )] (R F =CF 3 , CHF 2 , CH 2 CF 3 , CF 2 CH 3 ) yielded the corresponding alkyl derivatives [Mn(CO) 5 (R F )], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single‐crystal X‐ray diffraction studies. The solution‐phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn( 12 CO) 4 ( eq ‐ 13 CO)(R F )] and [Mn( 12 CO) 4 ( ax ‐ 13 CO)(R F )] isotopomers and a ranking of the R F donor power in the order CF 3