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dc.contributor.authorChalmers, Brian Alexander
dc.contributor.authorMeigh, Christina
dc.contributor.authorNejman, Phillip
dc.contributor.authorBuehl, Michael
dc.contributor.authorLebl, Tomas
dc.contributor.authorWoollins, J Derek
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorKilian, Petr
dc.date.accessioned2017-06-24T23:33:53Z
dc.date.available2017-06-24T23:33:53Z
dc.date.issued2016-07-18
dc.identifier243729568
dc.identifierc3c77594-ad70-4a8b-9262-3aa4543de8f4
dc.identifier84978696472
dc.identifier000380181400040
dc.identifier.citationChalmers , B A , Meigh , C , Nejman , P , Buehl , M , Lebl , T , Woollins , J D , Slawin , A M Z & Kilian , P 2016 , ' Geminally substituted tris(acenaphthyl) and bis(acenaphthyl) arsines, stibines and bismuthine : a structural and nuclear magnetic resonance investigation ' , Inorganic Chemistry , vol. 55 , no. 14 , pp. 7117-7125 . https://doi.org/10.1021/acs.inorgchem.6b01079en
dc.identifier.issn0020-1669
dc.identifier.otherORCID: /0000-0002-0269-3221/work/48131693
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131745
dc.identifier.otherORCID: /0000-0002-2999-2272/work/55901225
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861336
dc.identifier.otherORCID: /0000-0001-6379-3026/work/58285391
dc.identifier.otherORCID: /0000-0002-1498-9652/work/31779160
dc.identifier.urihttps://hdl.handle.net/10023/11076
dc.descriptionThis work was financially supported by the EPSRC and COST actions CM0802 PhoSciNet and SM1302 SIPs. The authors would like to thank the University of St Andrews NMR Service and the EPSRC UK National Mass Spectrometry Facility at Swansea University (NMSF).en
dc.description.abstractTris(acenaphthyl) and bis(acenaphthyl) substituted pnictogens (iPr2P-Ace)3E ( 2 – 4 ) (E = As, Sb, Bi; Ace = acenaphthene-5,6-diyl) and (iPr2P-Ace)2EPh ( 5 and 6 ), (E = As, Sb) were synthesised and fully characterised by multinuclear NMR, HRMS, elemental analysis and single crystal X-ray diffraction. The molecules adopt propeller-like geometries with the restricted rotational freedom of the sterically encumbered iPr2P-Ace groups resulting in distinct NMR features. In the tris(acenaphthyl) species ( 2 – 4 ) the phosphorus atoms are isochronous in the 31P{1H} NMR spectra, and the rotation of the three acenaphthyl moieties around E–Cipso bond is locked. On the other hand, the bis(acenaphthyl) species show a fluxional behaviour, resulting in an AX to A2 spin system transition in the 31P{1H} VT NMR spectra. This allowed elucidation of remarkable through-space couplings of 8TSJPP 11.5 Hz (for 5 ) and 25.8 Hz (for 6 ) at low temperature. In addition, detailed lineshape analysis of the thermodynamic parameters of the restricted rotation of the “propeller blades” in 5 was performed in the intermediate temperature region and also at coalescence. The lone pairs on the pnictogen atoms in 2 – 6 are oriented such that they form a bowl shaped area which is somehow buried within the molecule.
dc.format.extent9
dc.format.extent1392145
dc.format.extent1539417
dc.language.isoeng
dc.relation.ispartofInorganic Chemistryen
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subjectBDCen
dc.subject.lccQDen
dc.titleGeminally substituted tris(acenaphthyl) and bis(acenaphthyl) arsines, stibines and bismuthine : a structural and nuclear magnetic resonance investigationen
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.identifier.doi10.1021/acs.inorgchem.6b01079
dc.description.statusPeer revieweden
dc.date.embargoedUntil2017-06-24
dc.identifier.urlhttp://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.6b01079en


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