Electrostatic Presolvation Enables Selectivity in Photoinduced Ligand Exchange

Abstract Functional group compatibility remains a central challenge in photochemical C–H activation with metal complexes. Strongly donating groups preferentially coordinate to the reactive unsaturated metal and suppress weaker C–H coordination and σ-complex formation required for C–H bond activation. Controlling the initial coordination in photoinduced ligand exchange is therefore one approach to achieving selectivity in bond activation. Here, we resolve the elementary steps of photoinduced CO to acetonitrile ligand substitution for Rh(acac)(CO)2 with femtosecond-resolution X-ray absorption spectroscopy at the Rh L3-edge. We directly observe the formation of a hitherto undetected transient acetonitrile C–H σ-complex and its subsequent rearrangement to the thermodynamically favored nitrogen-coordinated solvent complex. Molecular dynamics simulations reveal that the initial C–H coordination is enabled by electrostatic presolvation, which orients the acetonitrile methyl groups toward the metal center prior to CO dissociation. Our results point to a general strategy to direct selectivity in C–H activation by controlling coordination through presolvation.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2026-11-09
DOI
https://doi.org/10.1021/jacs.6c17869
Primary Topic
Organometallic Complex Synthesis and Catalysis
Type
article
Field-Weighted Citation Impact
0.00

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article

Electrostatic Presolvation Enables Selectivity in Photoinduced Ligand Exchange

Dogeun Jang, Haneol Oh, Ambar Banerjee, Junho Lee et al.
Journal of the American Chemical Society
Organometallic Complex Synthesis and Catalysis
article

Electrostatic Presolvation Enables Selectivity in Photoinduced Ligand Exchange

Dogeun Jang, Haneol Oh, Ambar Banerjee, Junho Lee, Carl Caleman, Emiliano De Santis, Rory Ma, Raphael M. Jay, Philippe Wernet, Nils Huse, Tae Gyun Woo, Paulina Avilés, Minseok Kim, Yujin Kim, Jae Hyuk Lee, Timo Dederichs, Soo Min Cho, Tae Kyu Kim, Moritz Dybowski
article en

Abstract

Abstract Functional group compatibility remains a central challenge in photochemical C–H activation with metal complexes. Strongly donating groups preferentially coordinate to the reactive unsaturated metal and suppress weaker C–H coordination and σ-complex formation required for C–H bond activation. Controlling the initial coordination in photoinduced ligand exchange is therefore one approach to achieving selectivity in bond activation. Here, we resolve the elementary steps of photoinduced CO to acetonitrile ligand substitution for Rh(acac)(CO)2 with femtosecond-resolution X-ray absorption spectroscopy at the Rh L3-edge. We directly observe the formation of a hitherto undetected transient acetonitrile C–H σ-complex and its subsequent rearrangement to the thermodynamically favored nitrogen-coordinated solvent complex. Molecular dynamics simulations reveal that the initial C–H coordination is enabled by electrostatic presolvation, which orients the acetonitrile methyl groups toward the metal center prior to CO dissociation. Our results point to a general strategy to direct selectivity in C–H activation by controlling coordination through presolvation.

Journal of the American Chemical Society
University of Rome Tor Vergata (IT), Uppsala University (SE), Pohang University of Science and Technology (KR), Korea Advanced Institute of Science and Technology (KR), Universität Hamburg (DE), Deutsches Elektronen-Synchrotron DESY (DE), Istituto Nazionale di Fisica Nucleare, Roma Tor Vergata (IT), TCG Crest (IN), Centre For Research & Education in Science & Technology (IN)
National Research Foundation, Deutsche Forschungsgemeinschaft, Royal Swedish Academy of Sciences, National Research Foundation of Korea, Vetenskapsrådet, Ministry of Science and ICT, South Korea, Uppsala Multidisciplinary Center for Advanced Computational Science, National Cancer Institute
Organometallic Complex Synthesis and Catalysis
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