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Issue 4, 2017
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Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh

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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)RhCxFy 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.

Graphical abstract: Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh

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Publication details

The article was received on 08 Dec 2016, accepted on 16 Feb 2017 and first published on 16 Feb 2017


Article type: Edge Article
DOI: 10.1039/C6SC05391B
Citation: Chem. Sci., 2017,8, 3178-3186
  • Open access: Creative Commons BY license
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    Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh

    C. J. Pell, Y. Zhu, R. Huacuja, D. E. Herbert, R. P. Hughes and O. V. Ozerov, Chem. Sci., 2017, 8, 3178
    DOI: 10.1039/C6SC05391B

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