Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Tuning Ligand-Electronics in Iridium Pincer Complexes Enables Increased Activity in Acceptorless Alcohol Dehydrogenation

Spangenberg, Alice LU ; Karim, Samer ; Ahlquist, Mårten S.G. and Wendt, Ola F. LU (2026) In Organometallics 45(12). p.1368-1375
Abstract

Acceptorless alcohol dehydrogenation (AAD) converts alcohols to carbonyl compounds with concurrent hydrogen evolution, providing a sustainable and atom-efficient oxidation pathway. Here, we examine how electronic modifications of POCOP-type iridium pincer catalysts influence this transformation. A CF3-substituted complex exhibits a 3–7 times higher initial turnover frequency relative to the parent system in the dehydrogenation of 1-phenylethanol. Kinetic analysis shows that this enhancement reflects a lower intrinsic β-hydride elimination barrier, although slow hydrogen mass transfer partially masks the full activity advantage at elevated temperatures. These results establish ligand electronic manipulation as a direct method... (More)

Acceptorless alcohol dehydrogenation (AAD) converts alcohols to carbonyl compounds with concurrent hydrogen evolution, providing a sustainable and atom-efficient oxidation pathway. Here, we examine how electronic modifications of POCOP-type iridium pincer catalysts influence this transformation. A CF3-substituted complex exhibits a 3–7 times higher initial turnover frequency relative to the parent system in the dehydrogenation of 1-phenylethanol. Kinetic analysis shows that this enhancement reflects a lower intrinsic β-hydride elimination barrier, although slow hydrogen mass transfer partially masks the full activity advantage at elevated temperatures. These results establish ligand electronic manipulation as a direct method for accelerating AAD catalysis rather than merely improving stability.

(Less)
Please use this url to cite or link to this publication:
author
; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
45
issue
12
pages
8 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:105042427418
ISSN
0276-7333
DOI
10.1021/acs.organomet.6c00061
language
English
LU publication?
yes
id
c624b248-9877-441d-8e2d-2499d78f79a9
date added to LUP
2026-07-02 09:15:13
date last changed
2026-07-02 09:16:22
@article{c624b248-9877-441d-8e2d-2499d78f79a9,
  abstract     = {{<p>Acceptorless alcohol dehydrogenation (AAD) converts alcohols to carbonyl compounds with concurrent hydrogen evolution, providing a sustainable and atom-efficient oxidation pathway. Here, we examine how electronic modifications of POCOP-type iridium pincer catalysts influence this transformation. A CF<sub>3</sub>-substituted complex exhibits a 3–7 times higher initial turnover frequency relative to the parent system in the dehydrogenation of 1-phenylethanol. Kinetic analysis shows that this enhancement reflects a lower intrinsic β-hydride elimination barrier, although slow hydrogen mass transfer partially masks the full activity advantage at elevated temperatures. These results establish ligand electronic manipulation as a direct method for accelerating AAD catalysis rather than merely improving stability.</p>}},
  author       = {{Spangenberg, Alice and Karim, Samer and Ahlquist, Mårten S.G. and Wendt, Ola F.}},
  issn         = {{0276-7333}},
  language     = {{eng}},
  number       = {{12}},
  pages        = {{1368--1375}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Organometallics}},
  title        = {{Tuning Ligand-Electronics in Iridium Pincer Complexes Enables Increased Activity in Acceptorless Alcohol Dehydrogenation}},
  url          = {{http://dx.doi.org/10.1021/acs.organomet.6c00061}},
  doi          = {{10.1021/acs.organomet.6c00061}},
  volume       = {{45}},
  year         = {{2026}},
}