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dc.contributor.authorChalmers, Brian A.
dc.contributor.authorSomisara, Upulani
dc.contributor.authorSurgenor, Brian Andrew
dc.contributor.authorAthukorala Arachchige, Kasun S.
dc.contributor.authorWoollins, J Derek
dc.contributor.authorBuehl, Michael
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorKilian, Petr
dc.identifier.citationChalmers , 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 .
dc.identifier.otherPURE: 276612734
dc.identifier.otherPURE UUID: 033c693f-0900-4cbb-8f83-e97596362495
dc.identifier.otherORCID: /0000-0002-1095-7143/work/104252173
dc.identifier.otherORCID: /0000-0001-6379-3026/work/104252208
dc.identifier.otherORCID: /0000-0002-9527-6418/work/104252218
dc.identifier.otherORCID: /0000-0002-1498-9652/work/104252231
dc.identifier.otherORCID: /0000-0002-2999-2272/work/104252373
dc.identifier.otherScopus: 85120648691
dc.identifier.otherWOS: 000743203800001
dc.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.en
dc.description.abstractA 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
dc.rightsCopyright: © 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 (
dc.subjectSingle crystal X-ray structuresen
dc.subjectQD Chemistryen
dc.titleSynthetic and structural study of peri-substituted phosphine-arsinesen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.description.statusPeer revieweden

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