Laurence J. Taylor
Hydride Abstraction and Deprotonation - an Efficient Route to Low Coordinate Phosphorus and Arsenic Species
Taylor, Laurence J.; Bühl, Michael; Wawrzyniak, Piotr; Chalmers, Brian A.; Woollins, J. Derek; Slawin, Alexandra M.Z.; Fuller, Amy L.; Kilian, Petr
Authors
Michael Bühl
Piotr Wawrzyniak
Brian A. Chalmers
J. Derek Woollins
Alexandra M.Z. Slawin
Amy L. Fuller
Petr Kilian
Abstract
Treatment of Acenap(PiPr2)(EH2) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph3C·BF4 resulted in hydride abstraction to give [Acenap(PiPr2)(EH)][BF4] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low coordinate species Acenap(PiPr2)(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ4-phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ4-phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism. Hydride abstraction from a primary phosphine/arsine affords the first examples of secondary phosphino/arsino-phosphonium salts. Subsequent deprotonation provides a novel and high yielding route to phosphine-stabilised phosphinidene/arsinidene. These investigations indirectly support an ionic mechanism for the spontaneous dehydrogenation of the primary arsine.
Citation
Taylor, L. J., Bühl, M., Wawrzyniak, P., Chalmers, B. A., Woollins, J. D., Slawin, A. M., …Kilian, P. (2016). Hydride Abstraction and Deprotonation - an Efficient Route to Low Coordinate Phosphorus and Arsenic Species. European Journal of Inorganic Chemistry, 2016(5), 659-666. https://doi.org/10.1002/ejic.201500948
Journal Article Type | Article |
---|---|
Online Publication Date | Oct 6, 2015 |
Publication Date | Feb 1, 2016 |
Deposit Date | Apr 24, 2023 |
Publicly Available Date | Apr 28, 2023 |
Journal | European Journal of Inorganic Chemistry |
Print ISSN | 1434-1948 |
Electronic ISSN | 1099-0682 |
Publisher | Wiley |
Peer Reviewed | Peer Reviewed |
Volume | 2016 |
Issue | 5 |
Pages | 659-666 |
DOI | https://doi.org/10.1002/ejic.201500948 |
Public URL | https://nottingham-repository.worktribe.com/output/19789440 |
Publisher URL | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.201500948 |
Additional Information | This is the peer reviewed version of the following article: Taylor, L.J., Bühl, M., Wawrzyniak, P., Chalmers, B.A., Woollins, J.D., Slawin, A.M.Z., Fuller, A.L. and Kilian, P. (2016), Hydride Abstraction and Deprotonation – an Efficient Route to Low Coordinate Phosphorus and Arsenic Species. Eur. J. Inorg. Chem., 2016: 659-666, which has been published in final form at https://doi.org/10.1002/ejic.201500948 |
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