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 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CF₂ and (PNP)RhC(F)(CF₃). (PNP)RhCF₂ 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)RhCF₂ allowed unambiguous identification of the Rh product, [(PNP)Rh 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 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 CF₂, C₂F₄, and CF⁺ complexes and their hydrocarbon analogues.

SUBMITTER: Pell CJ 

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

REPOSITORIES: biostudies-literature