Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium.
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/8825392
- author
- Polukeev, Alexey LU ; Marcos, Rocío ; Ahlquist, Mårten S G and Wendt, Ola LU
- organization
- publishing date
- 2016-03-14
- 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
- Wiley-Blackwell
- external identifiers
-
- pmid:26880293
- wos:000372526500025
- pmid:26880293
- 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
- 2016-04-01 13:56:02
- date last changed
- 2022-06-10 02:43:17
@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}}, keywords = {{density functional calculations; hydrides; iridium; Pincer complexes; solvent effects}}, language = {{eng}}, month = {{03}}, number = {{12}}, pages = {{4078--4086}}, publisher = {{Wiley-Blackwell}}, 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}}, doi = {{10.1002/chem.201505133}}, volume = {{22}}, year = {{2016}}, }