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dc.contributor.authorArachchige, Kasun S. Athukorala
dc.contributor.authorCamacho, Paula Sanz
dc.contributor.authorRay, Matthew J.
dc.contributor.authorChalmers, Brian A.
dc.contributor.authorKnight, Fergus R.
dc.contributor.authorAshbrook, Sharon E.
dc.contributor.authorBuehl, Michael
dc.contributor.authorKilian, Petr
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorWoollins, J. Derek
dc.date.accessioned2015-05-25T23:10:52Z
dc.date.available2015-05-25T23:10:52Z
dc.date.issued2014-05-26
dc.identifier.citationArachchige , K S A , Camacho , P S , Ray , M J , Chalmers , B A , Knight , F R , Ashbrook , S E , Buehl , M , Kilian , P , Slawin , A M Z & Woollins , J D 2014 , ' Sterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactions ' , Organometallics , vol. 33 , no. 10 , pp. 2424-2433 . https://doi.org/10.1021/om500289ben
dc.identifier.issn0276-7333
dc.identifier.otherPURE: 134394111
dc.identifier.otherPURE UUID: 83dbf89d-c373-47cd-bd36-8963d451b9ee
dc.identifier.otherWOS: 000336642600004
dc.identifier.otherScopus: 84901404455
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131807
dc.identifier.otherORCID: /0000-0002-2999-2272/work/55901224
dc.identifier.otherORCID: /0000-0002-4538-6782/work/56638901
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861327
dc.identifier.otherORCID: /0000-0001-6379-3026/work/58285390
dc.identifier.otherORCID: /0000-0002-1498-9652/work/31779196
dc.identifier.otherWOS: 000336642600004
dc.identifier.urihttp://hdl.handle.net/10023/6690
dc.descriptionFunding: Engineering and Physical Sciences Research Council (EPSRC)en
dc.description.abstractFour related sterically restricted pen-substituted acenaphthenes have been prepared containing mixed tin phosphorus moieties in the proximal 5,6-positions (Acenap[SnR3][(PPr2)-Pr-i]; Acenap = acenaphthene-5,6-diyl; R-3 = Ph-3 (1), Ph2Cl (2), Me2Cl (3), Bu2Cl (4)). The degree of intramolecular P-Sn bonding within the series was investigated by X-ray crystallography, solution and solid-state NMR spectroscopy, and density functional theory (DFT/B3LYP/SBKJC/PCM) calculations. All members of the series adopt a conformation such that the phosphorus lone pair is located directly opposite the tin center, promoting an intramolecular donor acceptor P -> Sn type interaction. The extent of covalent bonding between Sn and P is found to be much greater in triorganotin chlorides 2-4 in comparison with the triphenyl derivative 1. Coordination of a highly electronegative chlorine atom naturally increases the Lewis acidity of the tin center, enhancing the Ip(P)-sigma*(Sn-Y) donor acceptor 3c-4e type interaction, as indicated by conspicuously short Sn-P peri distances and significant (1)J(P-31,Sn-119) spin spin coupling constants (SSCCs) in the range 740-754 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin spin coupling on the same order of magnitude as observed in solution. DFT calculations confirm the increased covalent bonding between P and Sn in 2-4, with notable WBIs of ca. 0.35 obtained, in comparison to 0.1 in 1.
dc.format.extent10
dc.language.isoeng
dc.relation.ispartofOrganometallicsen
dc.rights© 2014. American Chemical Society. © 2011 Taylor & Francis. This is an Accepted Manuscript of an article published in the Organometallics on 8 May 2014, available online: http://pubs.acs.org/doi/pdf/10.1021/om500289ben
dc.subjectNaphthalene peri positionsen
dc.subjectPolarizable continuum modelen
dc.subject4-center 6-electron bonden
dc.subject1st linear alignmenten
dc.subjectCrystal-structureen
dc.subjectMolecular-structureen
dc.subjectPhosphonium saltsen
dc.subjectLone-pairen
dc.subjectNonbonded interactionsen
dc.subjectDistance dependenceen
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleSterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactionsen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1021/om500289b
dc.description.statusPeer revieweden
dc.date.embargoedUntil2015-05-26


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