Booth, Rosalind, Whitwood, Adrian C. and Duhme-Klair, Anne-Kathrin orcid.org/0000-0001-6214-2459 (2024) The effect of ligand substituents on spectroscopic and catalytic properties of water-compatible Cp*Ir-(pyridinylmethyl)sulfonamide-based transfer hydrogenation catalysts. Inorganic Chemistry. ISSN 0020-1669
Abstract
Transition metal-based hydrogenation catalysts have applications ranging from high-value chemical synthesis to medicinal chemistry. A series of (pyridinylmethyl)sulfonamide ligands substituted with electron-withdrawing and -donating groups was synthesized to study the influence of the electronic contribution of the bidentate ligand in Cp*Ir piano-stool complexes. A variable temperature NMR investigation revealed a strong correlation between the electron-donating ability of the substituent and the rate of stereo-inversion of the complexes. This correlation was partially reflected in the catalytic activity of the corresponding catalysts. Complexes with electron-withdrawing substituents followed the trend observed in the variable temperature NMR study, thereby confirming the rate-determining step to be donation of the hydride ligand. Strongly electron-donating groups, on the other hand, caused a change in the rate-determining step to the formation of the iridium-hydride species. These results demonstrate that the activity of these catalysts can be tuned systematically via changes in the electronic contribution of the bidentate (pyridinylmethyl)sulfonamide ligands.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2024 The Authors. |
Dates: |
|
Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number UNSPECIFIED EP/T007338/1 BBSRC (BIOTECHNOLOGY AND BIOLOGICAL SCIENCES RESEARCH COUNCIL) BB/W011131/1 |
Depositing User: | Pure (York) |
Date Deposited: | 31 Jan 2024 16:20 |
Last Modified: | 06 Mar 2025 00:08 |
Published Version: | https://doi.org/10.1021/acs.inorgchem.3c04040 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/acs.inorgchem.3c04040 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:208493 |
Download
Description: Effectof LigandSubstituentson Spectroscopicand CatalyticPropertiesof Water-CompatibleCp*Ir-(pyridinylmethyl)sulfonamide-BasedTransferHydrogenationCatalysts
Licence: CC-BY 2.5