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dc.contributor.authorLi, H.
dc.contributor.authorAquino, A. J. A.
dc.contributor.authorCordes, D. B.
dc.contributor.authorHase, W. L.
dc.contributor.authorKrempner, C.
dc.identifier.citationLi , H , Aquino , A J A , Cordes , D B , Hase , W L & Krempner , C 2017 , ' Electronic nature of zwitterionic alkali metal methanides, silanides and germanides - a combined experimental and computational approach ' , Chemical Science , vol. 8 , no. 2 , pp. 1316-1328 .
dc.identifier.otherPURE: 247732416
dc.identifier.otherPURE UUID: d68ac6ae-6558-4786-b2be-f39da150e760
dc.identifier.otherRIS: urn:B6549844403E73CEBD3FD43B1C5456CB
dc.identifier.otherScopus: 85011066954
dc.identifier.otherORCID: /0000-0002-5366-9168/work/28233751
dc.descriptionThis project was funded in part by the NSF (grant no. 1407681; Project SusChEM: IUPAC) as part of the IUPAC International Funding Call on “Novel Molecular and Supramolecular Theory and Synthesis Approaches for Sustainable Catalysis”. Support was also provided by the TTU Department of Chemistry & Biochemistry cluster Robinson whose purchase was funded by the NSF (CRIF-MU CHE-0840493).en
dc.description.abstractZwitterionic group 14 complexes of the alkali metals of formula [C(SiMe2OCH2CH2OMe)3M], (M- 1 ), [Si(SiMe2OCH2CH2OMe)3M], (M- 2 ), [Ge(SiMe2OCH2CH2OMe)3M], (M- 3 ), where M = Li, Na or K, have been prepared, structurally characterized and their electronic nature was investigated by computational methods. Zwitterions M- 2 and M- 3 were synthesized via reactions of [Si(SiMe2OCH2CH2OMe)4] ( 2 ) and [Ge(SiMe2OCH2CH2OMe)4] ( 3 ) with MOBut (M = Li, Na or K), resp., in almost quantitative yields, while M- 1 were prepared from deprotonation of [HC(SiMe2OCH2CH2OMe)3] (1) with LiBut, NaCH2Ph and KCH2Ph, resp. X-ray crystallographic studies and DFT calculations in the gas-phase, including calculations of the NPA charges confirm the zwitterionic nature of these compounds, with the alkali metal cations being rigidly locked and charge separated from the anion by the internal OCH2CH2OMe donor groups. Natural bond orbital (NBO) analysis and the second order perturbation theory analysis of the NBOs reveal significant hyperconjugative interactions in M- 1 -M- 3 , primarily between the lone pair and the antibonding Si-O orbitals, the extent of which decreases in the order M- 1 > M- 2 > M- 3 . The experimental basicities and the calculated gas-phase basicities of M- 1 -M- 3 reveal the zwitterionic alkali metal methanides M- 1 to be significantly stronger bases than the analogous silanides M- 2 and germanium M- 3 .
dc.relation.ispartofChemical Scienceen
dc.rights© 2016 The Authors. Open Access article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.en
dc.subjectQD Chemistryen
dc.titleElectronic nature of zwitterionic alkali metal methanides, silanides and germanides - a combined experimental and computational approachen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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