Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)(5)(CORF)] (R-F=CF3, CHF2, CH2CF3, CF2CH3) 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((CO)-C-12)(4)(eq-(CO)-C-13)(R-F)] and [Mn((CO)-C-12)(4)(ax-(CO)-C-13)(R-F)] isotopomers and a ranking of the R-F donor power in the order CF3