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. 2025 May 12;16(24):10928-10934.
doi: 10.1039/d5sc02056e. eCollection 2025 Jun 18.

Activation of perfluoro(methyl vinyl ether) at Rh(i) complexes: metal-centered versus phosphine-mediated decarbonylation

Soodeh Mollasalehi  1 , Mike Ahrens  1 , Thomas Braun  1
Affiliations

Activation of perfluoro(methyl vinyl ether) at Rh(i) complexes: metal-centered versus phosphine-mediated decarbonylation

Soodeh Mollasalehi et al. Chem Sci. .

Abstract

This study investigates the reactivity of perfluoro(methyl vinyl ether) [PMVE, CF2[double bond, length as m-dash]CF(OCF3)] towards rhodium(i) phosphine complexes. The reaction pathways are characterized by C-O and C-F bond cleavage reactions and decarbonylation steps. On using the complex [Rh(H)(PEt3)3] (1), unprecedented reactivity pathways were observed that are distinct from those found for previously studied fluoroolefins. Reactivity of an excess PMVE at Rh is initiated by coordination to the Rh center in 1, followed by its insertion into the Rh-H bond and a β-OCF3 elimination. This process ultimately results in OCF3 ligand transformation to give trans-[Rh(F)(CO)(PEt3)3] (4) and Et3PF2. Reactions of stoichiometric amounts of PMVE with [Rh(H)(PEt3)3] (1) or an excess amount of it with [Rh(F)(PEt3)3] (6) led to olefin complex formation to yield trans-[Rh(F)(η2-CF2CFH)(PEt3)2] (7) and trans-[Rh(F)(CF(OCF3)CF2)(PEt3)2] (8), respectively. In contrast, a remarkable insertion into the Rh-F bond at [Rh(F)(CO)(PEt3)2] (4) was observed leading to the formation of trans-[Rh(CO)(CF(OCF3)CF3)(PEt3)2] (5). Decarbonylation of PMVE proceeds not only at Rh, but also via a metal-free, phosphine-mediated process. The latter is characterized by oxidative addition of PMVE at PEt3 to form the fluorophosphoranes E/Z-(F3CO)CF[double bond, length as m-dash]CF(PFEt3), which subsequently convert into Et3PF2, CO and presumably tetrafluoroethene.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Reactivity of complex 1 towards PMVE.
Scheme 2
Scheme 2. Mechanistic proposal for the reactivity of complex 1 towards PMVE.
Fig. 1
Fig. 1. DFT optimised structures ((B3LYP/cc-pvtz and cc-pvdz), see ESI†) of left: fac-[Rh(H){η2-CF2CF(OCF3)}(PMe3)3] (2*), and right: (2′*). Hydrogen atoms of the phosphine ligands are omitted for clarity.
Scheme 3
Scheme 3. Reactivity of complex 1 towards one equivalent of PMVE (top), and reactivity of complex 6 towards trifluoroethylene (bottom).
Scheme 4
Scheme 4. Reactivity of complex 6 towards PMVE.
Fig. 2
Fig. 2. DFT optimised structure (B3LYP/cc-pvdz) of complex 8. Hydrogen atoms of the phosphine ligands are omitted for clarity.
Scheme 5
Scheme 5. Reactivity of triethylphosphine towards: (i) perfluoro (methyl vinyl ether), and (ii) fluorophosgene.
Scheme 6
Scheme 6. Mechanistic proposal for the decomposition of the fluorophosphorane Z-(F3CO)CFCF(PFEt3).
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References

    1. Heath E. A. Int. Leg. Mater. 2017;56:193–205. doi: 10.1017/ilm.2016.2. - DOI
    1. Wallington T. J. Sulbaek Andersen M. P. Nielsen O. J. Chemosphere. 2015;129:135–141. doi: 10.1016/j.chemosphere.2014.06.092. - DOI - PubMed
    1. Sicard A. J. Baker R. T. Chem. Rev. 2020;120:9164–9303. doi: 10.1021/acs.chemrev.9b00719. - DOI - PubMed
    1. Manahan S. E., Fundamentals of environmental and toxicological chemistry: sustainable science, CRC press, 2013
    1. Kirsch P., Modern Fluoroorganic Chemistry: Synthesis, Reactivity and Applications, Wiley-VCH, Weinheim, 2nd edn, 2013

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