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Electron-Poor Iridium Pincer Complexes as Dehydrogenation Catalysts : Investigations into Deactivation through Formation of N2, CO, and Hydride Complexes

Spangenberg, Alice LU ; Kovalenko, Oleksandr O. LU ; Ahlquist, Mårten S.G. and Wendt, Ola F. LU (2024) In Organometallics 43(24). p.3242-3250
Abstract

A range of derivatives of an iridium pincer complex with a bis-trifluoromethyl-substituted ligand have been studied to determine how their properties differ from those of similar systems. The emphasis is on derivatives valuable for catalytic acceptorless dehydrogenation, including intermediates and deactivation products. The studies highlight small but important differences in the electron richness of the metal, as indicated by CO-stretching frequencies and hydride structures, as well as their impact on the equilibria between dihydride and tetrahydride species. T11JHD NMR studies and computational results highlight the effect of the electron-withdrawing groups on tetrahydride structures, indicating... (More)

A range of derivatives of an iridium pincer complex with a bis-trifluoromethyl-substituted ligand have been studied to determine how their properties differ from those of similar systems. The emphasis is on derivatives valuable for catalytic acceptorless dehydrogenation, including intermediates and deactivation products. The studies highlight small but important differences in the electron richness of the metal, as indicated by CO-stretching frequencies and hydride structures, as well as their impact on the equilibria between dihydride and tetrahydride species. T11JHD NMR studies and computational results highlight the effect of the electron-withdrawing groups on tetrahydride structures, indicating shortened H-H distances. Further, the equilibria of di- and tetrahydride species have been deduced using 2D-EXSY NMR spectroscopy, showing faster hydrogen elimination in the complex with electron-withdrawing groups incorporated into the ligand.

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author
; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
43
issue
24
pages
3242 - 3250
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85201880543
ISSN
0276-7333
DOI
10.1021/acs.organomet.4c00239
language
English
LU publication?
yes
id
96d7667b-3cf5-4da3-acf5-b6c73bb3a6b4
date added to LUP
2024-10-30 14:43:34
date last changed
2025-04-04 14:05:35
@article{96d7667b-3cf5-4da3-acf5-b6c73bb3a6b4,
  abstract     = {{<p>A range of derivatives of an iridium pincer complex with a bis-trifluoromethyl-substituted ligand have been studied to determine how their properties differ from those of similar systems. The emphasis is on derivatives valuable for catalytic acceptorless dehydrogenation, including intermediates and deactivation products. The studies highlight small but important differences in the electron richness of the metal, as indicated by CO-stretching frequencies and hydride structures, as well as their impact on the equilibria between dihydride and tetrahydride species. T<sub>1</sub><sup>1</sup>J<sub>HD</sub> NMR studies and computational results highlight the effect of the electron-withdrawing groups on tetrahydride structures, indicating shortened H-H distances. Further, the equilibria of di- and tetrahydride species have been deduced using 2D-EXSY NMR spectroscopy, showing faster hydrogen elimination in the complex with electron-withdrawing groups incorporated into the ligand.</p>}},
  author       = {{Spangenberg, Alice and Kovalenko, Oleksandr O. and Ahlquist, Mårten S.G. and Wendt, Ola F.}},
  issn         = {{0276-7333}},
  language     = {{eng}},
  number       = {{24}},
  pages        = {{3242--3250}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Organometallics}},
  title        = {{Electron-Poor Iridium Pincer Complexes as Dehydrogenation Catalysts : Investigations into Deactivation through Formation of N<sub>2</sub>, CO, and Hydride Complexes}},
  url          = {{http://dx.doi.org/10.1021/acs.organomet.4c00239}},
  doi          = {{10.1021/acs.organomet.4c00239}},
  volume       = {{43}},
  year         = {{2024}},
}