Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species
View/ Open
Date
2015Author
Grant ID
EP/E010695/1
EP/K031252/1
EP/K039210/1
Metadata
Show full item recordAbstract
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 co-ordinate 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.
Citation
Taylor , L J , Buehl , M , Wawrzyniak , P , Chalmers , B A , Woollins , J D , Slawin , A M Z , Fuller , A & Kilian , P 2015 , ' Hydride abstraction and deprotonation – an efficient route to low co-ordinate phosphorus and arsenic species ' , European Journal of Inorganic Chemistry , vol. Early view . https://doi.org/10.1002/ejic.201500948
Publication
European Journal of Inorganic Chemistry
Status
Peer reviewed
ISSN
1434-1948Type
Journal article
Description
This work was financially supported by the EPSRC and COST action grant CM1302 (SIPs).Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.