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

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.

• 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