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dc.date.accessioned2021-03-26T19:54:42Z
dc.date.created2021-02-03T23:11:01Z
dc.date.issued2020
dc.identifier.citationRaynaud, Christophe Norbert-Agaisse, Eliott James, Brian R. Eisenstein, Odile . 31P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere. Inorganic Chemistry. 2020, 59, 17038-17048
dc.identifier.urihttp://hdl.handle.net/10852/84958
dc.description.abstractThe NMR chemical shift has been the most versatile marker of chemical structures, by reflecting global and local electronic structures, and is very sensitive to any change within the chemical species. In this work, Ru(II) complexes with the same five ligands and a variable sixth ligand L (none, H2O, H2S, CH3SH, H2, N2, N2O, NO+, C═CHPh, and CO) are studied by using as the NMR reporter the phosphorus PA of a coordinated bidentate PA-N ligand (PA-N = o-diphenylphosphino-N,N′-dimethylaniline). The chemical shift of PA in RuCl2(PA-N)(PR3)(L) (R = phenyl, p-tolyl, or p-FC6H4) was shown to increase as the Ru–PA bond distance decreases, an observation that was not rationalized. This work, using density functional theory (DFT) calculations, reproduces reasonably well the observed 31P chemical shifts for these complexes and the correlation between the shifts and the Ru–PA bond distance as L varies. An interpretation of this correlation is proposed by using a natural chemical shift (NCS) analysis based on the natural bonding orbital (NBO) method. This analysis of the principal components of the chemical shift tensors shows how the σ-donating properties of L have a particularly high influence on the phosphine chemical shifts.
dc.languageEN
dc.publisherACS Publications
dc.title31P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere
dc.typeJournal article
dc.creator.authorRaynaud, Christophe
dc.creator.authorNorbert-Agaisse, Eliott
dc.creator.authorJames, Brian R.
dc.creator.authorEisenstein, Odile
dc.date.embargoenddate2021-11-06
cristin.unitcode185,15,12,70
cristin.unitnameHylleraas-senteret
cristin.ispublishedtrue
cristin.fulltextpostprint
cristin.qualitycode2
dc.identifier.cristin1886535
dc.identifier.bibliographiccitationinfo:ofi/fmt:kev:mtx:ctx&ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic Chemistry&rft.volume=59&rft.spage=17038&rft.date=2020
dc.identifier.jtitleInorganic Chemistry
dc.identifier.volume59
dc.identifier.issue23
dc.identifier.startpage17038
dc.identifier.endpage17048
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.0c02256
dc.identifier.urnURN:NBN:no-87653
dc.type.documentTidsskriftartikkel
dc.type.peerreviewedPeer reviewed
dc.source.issn0020-1669
dc.identifier.fulltextFulltext https://www.duo.uio.no/bitstream/handle/10852/84958/2/Phosphine%2BNMR-accepted%2Bversion%2BInorg%2BChem%2B.pdf
dc.type.versionAcceptedVersion
dc.relation.projectNFR/262695


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