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dc.contributor.authorDiamond, Louise
dc.contributor.authorKnight, Fergus Ross
dc.contributor.authorCordes, David Bradford
dc.contributor.authorWard, Andrew Christopher Clifford
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorWoollins, J Derek
dc.identifier.citationDiamond , L , Knight , F R , Cordes , D B , Ward , A C C , Slawin , A M Z & Woollins , J D 2015 , ' Acenaphtho[5,6-cd]-1,2-dichalcogenoles and their platinum complexes ' , Polyhedron , vol. 85 , pp. 395-404 .
dc.identifier.otherPURE: 169383491
dc.identifier.otherPURE UUID: 322f3d6b-c468-4ca6-a410-671b38a1b212
dc.identifier.otherWOS: 000347582900050
dc.identifier.otherORCID: /0000-0002-5366-9168/work/28024019
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861392
dc.identifier.otherORCID: /0000-0002-1498-9652/work/31779189
dc.identifier.otherScopus: 84907656701
dc.descriptionThe work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC).en
dc.description.abstractA related series of bis(phosphine) platinum complexes 1–5 and 6–8 bearing dichalcogenate acenaphthylene ligands have been synthesised. The chalcogen–chalcogen bonds in the parent acenaphtho[5,6-cd]-1,2-dichalcogenoles (AcenapylE2; L1 E = S, L2 E = Se; Acenapyl = acenaphthylene-5,6-diyl) were reduced with two equivalents of lithium triethylborohydride to form the dilithio-species. Metathetical addition of the lithium dichalcogenate species to a suspension of the appropriate cis-dichlorobis(phosphine)platinum in THF resulted in the formation of platinum(II) complexes [Pt(5,6-AcenapylE2)(PR3)2] (1 E = S, R3 = Ph3; 2 E = S, R3 = Ph2Me; 3 E = S, R3 = PhMe2; 4 E = S, R3 = Me3; 6 E = Se, R3 = Ph3; 7 E = Se, R3 = Ph2Me; 8 E = Se, R3 = PhMe2). The dilithio-species of L1 and L2 were also reacted with (1,5-cyclooctadiene)platinum(II) dichloride. This reaction was successful with L1 resulting in the formation of platinum complex [Pt(5,6-AcenapylS2)(COD)] (5). Complexes 1–3 and 5–8 have been fully characterised, principally by multinuclear magnetic resonance spectroscopy, IR and MS. Secondary isotopomer effects create complex satellite systems observed in both the 31P{1H} NMR and 77Se NMR spectra of selenium complexes 6–8. X-ray structures were determined for L1, 1, 3 and 6 and analysed, where appropriate, by measuring the peri-distance, splay angle magnitude, peri-atom displacement, central naphthalene ring torsions and the geometry around the platinum centre. Platinum was found to adopt a distorted square-planar geometry in all three complexes. Complex 1 was found to have the greatest molecular distortion of all three complexes, showing that changing the phosphine group and also the chalcogen has a noticeable effect. Comparisons were made between 6 and our previously reported [Pt(NapSe2)(PPh3)2] and [Pt(AcenapSe2)(PPh3)2] complexes; the level of distortion was found to decrease as the backbone is altered from naphthalene to acenaphthylene.
dc.rightsCrown copyright © 2014 Published by Elsevier Ltd. All rights reserved. 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:
dc.subjectX-ray structureen
dc.subjectCoordination complexen
dc.subjectQD Chemistryen
dc.titleAcenaphtho[5,6-cd]-1,2-dichalcogenoles and their platinum complexesen
dc.typeJournal articleen
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.description.statusPeer revieweden

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