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dc.contributor.authorSurgenor, Brian Andrew
dc.contributor.authorChalmers, Brian Alexander
dc.contributor.authorAthukorala Arachchige, Kasun Sankalpa
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorWoollins, J Derek
dc.contributor.authorBuehl, Michael
dc.contributor.authorKilian, Petr
dc.date.accessioned2016-04-01T12:30:04Z
dc.date.available2016-04-01T12:30:04Z
dc.date.issued2014-06-09
dc.identifier.citationSurgenor , B A , Chalmers , B A , Athukorala Arachchige , K S , Slawin , A M Z , Woollins , J D , Buehl , M & Kilian , P 2014 , ' Reactivity profile of a peri-substitution-stabilized phosphanylidene-phosphorane : synthetic, structural, and computational studies ' Inorganic Chemistry , vol. 53 , no. 13 , pp. 6856–6866 . https://doi.org/10.1021/ic500697men
dc.identifier.issn0020-1669
dc.identifier.otherPURE: 192593970
dc.identifier.otherPURE UUID: 55aafa89-9d2e-45d8-a8c9-3fc28d537605
dc.identifier.otherScopus: 84904024973
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131787
dc.identifier.otherORCID: /0000-0002-2999-2272/work/55901233
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861826
dc.identifier.otherORCID: /0000-0001-6379-3026/work/58285410
dc.identifier.otherORCID: /0000-0002-1498-9652/work/31779195
dc.identifier.otherWOS: 000338748100052
dc.identifier.urihttp://hdl.handle.net/10023/8537
dc.descriptionThe authors thank the EaStChem, EPSRC, and the COST actions CM0802 PhoSciNet and CM1302 SIPs for financial support.en
dc.description.abstractThe reactions of peri-substitution-stabilized phosphanylidene-phosphorane 1 with [AuCl(tht)] or [PtCl2(cod)] afford binuclear complexes [((1)(AuCl)2)2] 2 and [((1)(PtCl2))2] 3, in which four electrons of the ligand are used in bonding to two metal atoms in the bridging arrangement. Reactions of 1 with [Mo(CO)4(nbd)] or (RhCl2Cp*)2 afford mononuclear complexes [(1)2Mo(CO)4] 4 and [(1)RhCl2Cp*] 5, in which two electrons of the ligand are used to form terminal complexes. Formation of these complexes disrupts the negative hyperconjugation at the P–P bond to various extents, which is mirrored by variations in their P–P bond distances (2.179(4)–2.246(4) Å). The P–P bond is ruptured upon formation of Pd diphosphene complex 6, which is likely to proceed through a phosphinidene intermediate. In air, 1 is fully oxidized to phosphonic acid 7. Reactions of 1 with chalcogens under mild conditions generally afford mixtures of products, from which the trithionated 8, dithionated 9, diselenated 10, and monotellurated 11 species were isolated. The bonding in the chalcogeno derivatives is discussed using DFT (B3LYP) and natural bond orbital analysis, which indicate a contribution from dative bonding in 8–10. The buttressing effect of the peri backbone is shown to be an essential factor in the formation of the single push–double-pull bis(borane) 13. This is demonstrated experimentally through a synthesis parallel to that used to make 13, but lacking the backbone, which leads to different products. The P–P bond distances in the reported products, as well as additional species, are correlated with Wiberg bond indices, showing very good agreement for a variety of bonding modes, including the negative hyperconjugation.
dc.format.extent11
dc.language.isoeng
dc.relation.ispartofInorganic Chemistryen
dc.rightsCopyright © 2014 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1021/ic500697men
dc.rightsCopyright © 2014 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1021/ic500697men
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleReactivity profile of a peri-substitution-stabilized phosphanylidene-phosphorane : synthetic, structural, and computational studiesen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.Office of the Principalen
dc.identifier.doihttps://doi.org/10.1021/ic500697m
dc.description.statusPeer revieweden
dc.identifier.urlhttp://pubs.acs.org/doi/suppl/10.1021/ic500697men


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