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dc.contributor.authorOrtuno, Manuel A.
dc.contributor.authorCastro, Ludovic
dc.contributor.authorBuehl, Michael
dc.identifier.citationOrtuno , M A , Castro , L & Buehl , M 2013 , ' Computational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexes ' Organometallics , vol. 32 , no. 21 , pp. 6437-6444 . DOI: 10.1021/om400774yen
dc.identifier.otherPURE: 105530942
dc.identifier.otherPURE UUID: 20a69c48-1c56-4d8d-9ac8-e86757e7692f
dc.identifier.otherWOS: 000326955700037
dc.identifier.otherScopus: 84887679682
dc.description.abstract103RhNMR chemical shifts have been computed at the GIAO-B3LYP level of density functional theory (DFT) for a number of [Rh(COD)(P∩P)]+ complexes [COD = 1,5-cyclooctadiene, P∩P = chelating bis(phosphine) including bis(dimethylphosphino)ethane (dmpe), bis(diphenylphosphino)ethane (dmpe), MeDUPHOS, DIOP, BINAP, and others]. Structures have been optimized using PBE0 and M06 functionals in the gas phase, in a continuum modeling the solvent, and with [PF6]− counteranion included explicitly. Observed trends in δ(103Rh) are well reproduced for pristine PBE0-optimized cations in the gas phase or for ion pairs optimized in a continuum with M06. While there is no overall trend between computed δ(103Rh) values and complex stabilities (evaluated through isodesmic ligand exchange reactions), there is a linear relationship between the 103Rh chemical shifts and the mean Rh–P bond distances. This relationship appears to be remarkably general, encompassing various chelating ring sizes and substituents at P, including remote electron-donating and -withdrawing substituents that are characterized through their Hammett constants. The combination of 103Rh NMR and DFT computations emerges as a useful tool for structure elucidation of Rh–phosphine complexes.en
dc.rightsCopyright 2013, American Chemical Society. This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Organometallics after peer review. To access the final edited and published work, see
dc.subjectDensity-functional theoryen
dc.subjectMolecular orbital methodsen
dc.subjectNMR spectroscopyen
dc.subjectBasis setsen
dc.subjectOrganometallic complexesen
dc.subjectNoncovalent interactionsen
dc.subjectDiolefin complexesen
dc.subjectShielding tensorsen
dc.subjectOlefin complexesen
dc.titleComputational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexesen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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