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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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Supplementary files

Article information


Submitted
08 Dec 2016
Accepted
16 Feb 2017
First published
16 Feb 2017

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2017,8, 3178-3186
Article type
Edge Article

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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