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Issue 41, 2017
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Synthesis and oxidation of phosphine cations

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Cationic phosphines of the form [(L)PPh2]+ are prepared by reaction of Ph2PCl with carbenes (L) including a chiral bis(oxazoline)-based carbene, a cyclic(alkyl)(amino) carbene (cAAC), and a 1,2,3-triazolium-derived carbene, affording the products, [(IBox-iPr2)PPh2][OSO2CF3] 1, [(cAAC)PPh2][OSO2CF3] 2 and [((TripCH2N2(NMe)C2Ph)PPh2)2(AgCl)2][Cl]23. Using PhPCl2, the related dication [CH2(NC3H2NDipp)2PPh]2+4 was also prepared. Crystallographically-determined metric parameters and computational data indicate that these species are best described as cationic phosphines rather than phosphenium cations. The oxidation of these cations with XeF2 afforded [(IBox-iPr2)PF2Ph2][OSO2CF3] 5, [(cAAC)PF2Ph2][OSO2CF3] 6 and [(TripCH2N2(NMe)C2Ph)PF2Ph2][Cl] 7; 4 was not oxidized. These observations are understood by a computational assessment of the average local ionisation potentials at valence shell charge concentrations identified via topological analysis of the electron density.

Graphical abstract: Synthesis and oxidation of phosphine cations

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Article information

28 Aug 2017
27 Sep 2017
First published
28 Sep 2017

Dalton Trans., 2017,46, 14149-14157
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Synthesis and oxidation of phosphine cations

M. Mehta, T. C. Johnstone, J. Lam, B. Bagh, A. Hermannsdorfer, M. Driess and D. W. Stephan, Dalton Trans., 2017, 46, 14149
DOI: 10.1039/C7DT03175K

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