Photochemical Oxygen‐Atom‐Transfer Reactivity of Platinum(II) Peroxycarbonates
- 1Department of Chemistry and Chemical Biology Harvard University Cambridge Massachusetts USA
- 2Present address: Department of Chemistry Northwestern University Evanston Illinois USA
Abstract
Peroxycarbonate (CO4 2–) is implicated in various biological, catalytic, and energy storage processes – despite the capability of transition metals to guide the reactivity of this unstable intermediate toward productive ends, the coordination chemistry of metal–peroxycarbonate complexes, M(CO4), remains poorly understood. Herein, we describe the synthesis, isolation, and structural characterization of two platinum(II) peroxycarbonate complexes Pt(PPh3)2(CO4) (1) and Pt(dppe)(CO4) (2) (dppe = 1,2‐bis(diphenylphosphino)ethane). Whereas the complexes are thermally stable, they react by oxygen‐atom transfer (OAT) when irradiated with visible light. This photoreactivity was investigated using NMR and FT‐IR photolysis to identify structures of reaction intermediates and photoproducts, together with kinetic analyses, which establish unimolecular OAT from the CO4 2− ligand to the bound phosphine. In addition to providing rare examples of structurally characterized M(CO4) complexes, this work is the first demonstration of photochemical reactivity in a peroxycarbonate complex.
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BibTeX
@article{sullivan2026photochemical,
title = {{Photochemical Oxygen‐Atom‐Transfer Reactivity of Platinum(II) Peroxycarbonates}},
author = {Meghan G. Sullivan and Jesse B. Gordon and Brandon M. Campbell and Shao‐Liang Zheng and Daniel G. Nocera},
journal = {Angewandte Chemie (International Ed. in English)},
year = {2026},
month = sep,
doi = {10.1002/anie.5181266},
url = {https://doi.org/10.1002/anie.5181266},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Photochemical Oxygen‐Atom‐Transfer Reactivity of Platinum(II) Peroxycarbonates
AU - Meghan G. Sullivan
AU - Jesse B. Gordon
AU - Brandon M. Campbell
AU - Shao‐Liang Zheng
AU - Daniel G. Nocera
PY - 2026
DA - 2026/09/24
JO - Angewandte Chemie (International Ed. in English)
DO - 10.1002/anie.5181266
UR - https://doi.org/10.1002/anie.5181266
AB - Peroxycarbonate (CO4 2–) is implicated in various biological, catalytic, and energy storage processes – despite the capability of transition metals to guide the reactivity of this unstable intermediate toward productive ends, the coordination chemistry of metal–peroxycarbonate complexes, M(CO4), remains poorly understood. Herein, we describe the synthesis, isolation, and structural characterization of two platinum(II) peroxycarbonate complexes Pt(PPh3)2(CO4) (1) and Pt(dppe)(CO4) (2) (dppe = 1,2‐bis(diphenylphosphino)ethane). Whereas the complexes are thermally stable, they react by oxygen‐atom transfer (OAT) when irradiated with visible light. This photoreactivity was investigated using NMR and FT‐IR photolysis to identify structures of reaction intermediates and photoproducts, together with kinetic analyses, which establish unimolecular OAT from the CO4 2− ligand to the bound phosphine. In addition to providing rare examples of structurally characterized M(CO4) complexes, this work is the first demonstration of photochemical reactivity in a peroxycarbonate complex.
SN - 1433-7851
SN - 1521-3773
ER -