Synthetic and structural study of peri-substituted phosphine-arsines
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A series of phosphorus-arsenic peri-substituted acenaphthene species have been isolated and fully characterised, including single crystal X-ray diffraction. Reactions of EBr3 (E = P, As) with iPr2PAcenapLi (Acenap = acenaphthene-5,6-diyl) afforded the thermally stable peri-substitution supported donor–acceptor complexes, iPr2PAcenapEBr2 3 and 4 . Both complexes show a strong P→E dative interaction, as observed by X-ray crystallography and 31P NMR spectroscopy. DFT calculations indicated the unusual As∙∙∙As contact (3.50 Å) observed in the solid state structure of 4 results from dispersion forces rather than metallic interactions. Incorporation of the excess AsBr3 in the crystal structure of 3 promotes the formation of the ion separated species [iPr2PAcenapAsBr]+Br− 5 . A decomposition product 6 containing the rare [As6Br8]2– heterocubane dianion was isolated and characterised crystallographically. The reaction between iPr2PAcenapLi and EtAsI2 afforded tertiary arsine (BrAcenap)2AsEt 7 , which was subsequently lithiated and reacted with PhPCl2 and Ph2PCl to afford cyclic PhP(Acenap)2AsEt 8 and acyclic EtAs(AcenapPPh2)2 9
Chalmers , B A , Somisara , U , Surgenor , B A , Athukorala Arachchige , K S , Woollins , J D , Buehl , M , Slawin , A M Z & Kilian , P 2021 , ' Synthetic and structural study of peri -substituted phosphine-arsines ' , Molecules , vol. 26 , no. 23 , 7222 . https://doi.org/10.3390/molecules26237222
Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
DescriptionThe authors thank the Engineering and Physical Sciences Research Council (EPSRC, Grant EP/J500549/1 and EP/M506631/1), COST action CM1302 SIPs and CM0802, and the EaStCHEM School of Chemistry for support.
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