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Polukeev AV, Marcos R, Ahlquist MS, et al. Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium. Chemistry. 2016;22(12):4078-86doi: 10.1002/chem.201505133.
Polukeev, A. V., Marcos, R., Ahlquist, M. S., & Wendt, O. F. (2016). Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium. Chemistry (Weinheim an der Bergstrasse, Germany), 22(12), 4078-86. https://doi.org/10.1002/chem.201505133
Polukeev, Alexey V, et al. "Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 22,12 (2016): 4078-86. doi: https://doi.org/10.1002/chem.201505133
Polukeev AV, Marcos R, Ahlquist MS, Wendt OF. Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium. Chemistry. 2016 Mar 14;22(12):4078-86. doi: 10.1002/chem.201505133. Epub 2016 Feb 16. PMID: 26880293.
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Chemistry. 2016 Mar 14;22(12):4078-86. doi: 10.1002/chem.201505133. Epub 2016 Feb 16.

Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium.

Chemistry (Weinheim an der Bergstrasse, Germany)

Alexey V Polukeev, Rocío Marcos, Mårten S G Ahlquist, Ola F Wendt

Affiliations

  1. Centre for Analysis and Synthesis, Department of Chemistry, Lund University, PO Box 124, 22100, Lund, Sweden.
  2. Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, 106 91, Stockholm, Sweden.
  3. Centre for Analysis and Synthesis, Department of Chemistry, Lund University, PO Box 124, 22100, Lund, Sweden. [email protected].

PMID: 26880293 DOI: 10.1002/chem.201505133

Abstract

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, JHD and T1(min), with rHH increasing upon moving to more polar medium. The only known example of such behaviour (complex [(POCOP)IrH2], POCOP=2,6-(tBu2PO)2C6H3) 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 α-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.

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: density functional calculations; hydrides; iridium; pincer complexes; solvent effects

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