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(3) and C(2)HF(5) produced perfluoroalkylidene complexes (PNP)Rh[double bond, length as m-dash]CF(2) and (PNP)Rh[double bond, length as m-dash]C(F)(CF(3)). (PNP)Rh[double bond, length as m-dash]CF(2) could also be obtained via the reaction of (PNP)Rh(TBE) with Me(3)SiCF(3)/CsF, with an admixture of (PNP)Rh(C(2)F(4)), where TBE = tert-butylethylene. Abstraction of fluoride from these neutral (PNP)RhC( x )F( y ) complexes was successful, although only abstraction from (PNP)Rh[double bond, length as m-dash]CF(2) 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(C(2)F(4)) and [(PNP)Rh(C(2)F(3))](+) isomers as well as comparisons between the electronic structure of the [double bond, length as m-dash]CF(2), C(2)F(4), and [triple bond, length as m-dash]CF(+) complexes and their hydrocarbon analogues.