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

Polukeev, Alexey LU ; Marcos, Rocío; Ahlquist, Mårten S G and Wendt, Ola LU (2016) In Chemistry - A European Journal 22(12). p.4078-4086
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-(tBu2 PO)2 C6 H3 ) 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... (More)
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-(tBu2 PO)2 C6 H3 ) 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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
density functional calculations, hydrides, iridium, Pincer complexes, solvent effects
in
Chemistry - A European Journal
volume
22
issue
12
pages
9 pages
publisher
John Wiley & Sons
external identifiers
  • pmid:26880293
  • wos:000372526500025
  • scopus:84975763633
ISSN
1521-3765
DOI
10.1002/chem.201505133
language
English
LU publication?
yes
id
a43f95e9-febb-4f16-a11a-9b97a6b5104e (old id 8825392)
date added to LUP
2016-03-07 16:08:37
date last changed
2017-09-24 04:02:18
@article{a43f95e9-febb-4f16-a11a-9b97a6b5104e,
  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-(tBu2 PO)2 C6 H3 ) 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.},
  author       = {Polukeev, Alexey and Marcos, Rocío and Ahlquist, Mårten S G and Wendt, Ola},
  issn         = {1521-3765},
  keyword      = {density functional calculations,hydrides,iridium,Pincer complexes,solvent effects},
  language     = {eng},
  month        = {03},
  number       = {12},
  pages        = {4078--4086},
  publisher    = {John Wiley & Sons},
  series       = {Chemistry - A European Journal},
  title        = {Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium.},
  url          = {http://dx.doi.org/10.1002/chem.201505133},
  volume       = {22},
  year         = {2016},
}