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Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1553-4027
2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 12, 4078-4086 p.Article in journal (Refereed) PublishedText
Abstract [en]

The hydride iridium pincer complex [(PCyP)IrH2] (PCyP=cis-1,3-bis[(di-tert-butylphosphino)methyl]cyclohexane, 1) reveals remarkably solvent-dependent hydride chemical shifts, isotope chemical shifts, J(HD) and T-1(min), with r(HH) increasing upon moving to more polar medium. The only known example of such behaviour (complex [(POCOP)IrH2], POCOP=2,6-(tBu(2)PO)(2)C6H3) was explained by the coordination of a polar solvent molecule to the iridium (J. Am. Chem. Soc. 2006, 128, 17114). Based on the existence of an agostic bond between -C-H and iridium in 1 in all solvents, we argue that the coordination of solvent can be rejected. DFT calculations revealed that the structures of 1 and [(POCOP)IrH2] depend on the dielectric permittivity of the medium and these compounds adopt trigonal-bipyramidal geometries in non-polar media and square-pyramidal geometries in polar media.

Place, publisher, year, edition, pages
Wiley-VCH Verlag , 2016. Vol. 22, no 12, 4078-4086 p.
Keyword [en]
density functional calculations, hydrides, iridium, pincer complexes, solvent effects
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-185640DOI: 10.1002/chem.201505133ISI: 000372526500025PubMedID: 26880293ScopusID: 2-s2.0-84959866485OAI: diva2:923646
Swedish Research CouncilKnut and Alice Wallenberg Foundation

QC 20160427

Available from: 2016-04-27 Created: 2016-04-25 Last updated: 2016-04-27Bibliographically approved

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Marcos, RocioAhlquist, Mårten S. G.
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