Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh.

ABSTRACT: 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 CHF₃ and C₂HF₅ produced perfluoroalkylidene complexes (PNP)Rh[double bond, length as m-dash]CF₂ and (PNP)Rh[double bond, length as m-dash]C(F)(CF₃). (PNP)Rh[double bond, length as m-dash]CF₂ could also be obtained via the reaction of (PNP)Rh(TBE) with Me₃SiCF₃/CsF, with an admixture of (PNP)Rh(C₂F₄), 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]CF₂ 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(C₂F₄) and [(PNP)Rh(C₂F₃)]⁺ isomers as well as comparisons between the electronic structure of the [double bond, length as m-dash]CF₂, C₂F₄, and [triple bond, length as m-dash]CF⁺ complexes and their hydrocarbon analogues.

SUBMITTER: Pell CJ 

PROVIDER: S-EPMC5414389 | biostudies-literature | 2017 Apr

REPOSITORIES: biostudies-literature