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Issue 45, 2015
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Perfluoropropenyl-containing phosphines from HFC replacements

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Abstract

A series of new perfluoropropenyl-containing phosphines of the type R3−nP(E-CF[double bond, length as m-dash]CFCF3)n (R = Ph, iPr, n = 1, 2; R = tBu, n = 2) have been prepared from the reaction of the hydrofluoroolefin Z-CF3CF[double bond, length as m-dash]CFH (HFO-1225ye) with base and the appropriate chlorophosphine, while reaction with Cl2PCH2CH2PCl2 gave (CF3CF[double bond, length as m-dash]CF)2PCH2CH2P(CF[double bond, length as m-dash]CFCF3)2, the first example of a bidentate perfluoroalkenyl-containing phosphine. An alternative route to these phosphines based on the room- or low-temperature deprotonation of CF3CF2CH2F (HFC-236ea) gives mainly the E-isomer, but also a small amount of the Z-isomer, the ratio of which depends on the reaction temperature. All of the phosphines could be readily oxidised with either H2O2 or urea·H2O2, and the phosphine selenides R3−nP(Se)(E-CF[double bond, length as m-dash]CFCF3)n (R = Ph, n = 1,2; R = iPr, n = 1; R = tBu, n = 2) were also prepared. The steric and electronic properties of these ligands were determined based on their platinum(II), palladium(II) and molybdenum carbonyl complexes. The crystal structures of (CF3CF[double bond, length as m-dash]CF)2PCH2CH2P(CF[double bond, length as m-dash]CFCF3)2, (CF3CF[double bond, length as m-dash]CF)2P(O)CH2CH2P(O)(CF[double bond, length as m-dash]CFCF3)2, iPr2P(Se)(CF[double bond, length as m-dash]CFCF3)2, trans-[PtCl2{Ph(3−n)P(E-CF[double bond, length as m-dash]CFCF3)n}2] (n = 1 or 2), trans-[PdCl2{R2P(E-CF[double bond, length as m-dash]CFCF3)}2] (R = Ph, iPr) and [Mo(CO)4{(CF3CF[double bond, length as m-dash]CF)2PCH2CH2P(CF[double bond, length as m-dash]CFCF3)2}] are reported.

Graphical abstract: Perfluoropropenyl-containing phosphines from HFC replacements

  • This article is part of the themed collection: Fluorine
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Publication details

The article was received on 29 May 2015, accepted on 15 Jul 2015 and first published on 27 Jul 2015


Article type: Paper
DOI: 10.1039/C5DT02043C
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 19717-19731
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    Perfluoropropenyl-containing phosphines from HFC replacements

    A. K. Brisdon, H. Ali Ghaba, B. Beutel, A. Egjandi, A. Addaraidi and R. G. Pritchard, Dalton Trans., 2015, 44, 19717
    DOI: 10.1039/C5DT02043C

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