Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh.

The manuscript reports the synthesis, characterization, and analysis of electronic structure in a series of complexes of small perfluorocarbon ligands with the (PNP)Rh fragment (where PNP is a diarylamido/bis(phosphine) pincer ligand). Reactions of (PNP)Rh(TBE) as the source of (PNP)Rh with CHF and CHF produced perfluoroalkylidene complexes (PNP)Rh[double bond, length as m-dash]CF and (PNP)Rh[double bond, length as m-dash]C(F)(CF). (PNP)Rh[double bond, length as m-dash]CF could also be obtained the reaction of (PNP)Rh(TBE) with MeSiCF/CsF, with an admixture of (PNP)Rh(CF), where TBE = -butylethylene. Abstraction of fluoride from these neutral (PNP)RhC F complexes was successful, although only abstraction from (PNP)Rh[double bond, length as m-dash]CF allowed unambiguous identification of the Rh product, [(PNP)Rh[triple bond, length as m-dash]CF]. DFT computational studies allowed comparison of relative energies of (PNP)Rh(CF) and [(PNP)Rh(CF)] isomers as well as comparisons between the electronic structure of the [double bond, length as m-dash]CF, CF, and [triple bond, length as m-dash]CF complexes and their hydrocarbon analogues.