Reactions of U(DMSO)₈(ClO₄)₄ with Terpyridine Yield Dimeric Hydrolysis Products and Induce C-C Coupling
Abstract
Reactions have been carried out using UIV(DMSO)₈(ClO₄)₄ with 2,2′:6′,2′′-terpyridine (terpy) under non-aqueous conditions. At room temperature in acetonitrile, the combination of the U(IV) starting material with terpy resulted in a mixture containing [UO₂(DMSO)₂terpy][ClO₄]₂·MeCN, while increasing the water content led to the hydrolysis products [(UO₂(DMSO)terpy)₂(μ₂–O)][ClO₄]₂ and [(UO₂terpy)₂(μ₂–OH)₂][ClO₄]₂·MeCN·H₂O. Performing the reaction at slightly elevated temperature with no added water led to the formation of [UO₂sexipyridine][ClO₄]₂·MeCN. This new uranyl complex contains the hexadentate ligand 2,2′:6′,2′′:6′′,2′′:6′′′,2′′′′:6′′′′,2′′′′′-sexipyridine, which formed in situ from the tetravalent uranium starting material, where photoexcited uranyl or in situ generated peroxide could have induced C–C coupling. Analysis of bonding in the dimeric uranyl species via quantum chemical methods revealed a small increase in covalency of the bridging oxo unit and a slightly greater stability, compared to the bridging hydroxo compound, which causes a significant shift uranyl symmetric stretch in the Raman spectrum. Structural, spectroscopic, and computational comparisons are made across the series of compounds, providing insight into the bonding and reactivity of uranium in non-aqueous media.
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BibTeX
@article{mikeska2026reactions,
title = {{Reactions of U(DMSO)₈(ClO₄)₄ with Terpyridine Yield Dimeric Hydrolysis Products and Induce C-C Coupling}},
author = {Emily R. Mikeska and Richard E. Wilson and Valérie Vallet},
journal = {Inorganic Chemistry},
year = {2026},
month = jun,
doi = {10.1021/acs.inorgchem.5c05930},
url = {https://hal.science/hal-05639573v1},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - JOUR
TI - Reactions of U(DMSO)₈(ClO₄)₄ with Terpyridine Yield Dimeric Hydrolysis Products and Induce C-C Coupling
AU - Emily R. Mikeska
AU - Richard E. Wilson
AU - Valérie Vallet
PY - 2026
DA - 2026/06/22
JO - Inorganic Chemistry
DO - 10.1021/acs.inorgchem.5c05930
UR - https://hal.science/hal-05639573v1
AB - Reactions have been carried out using UIV(DMSO)₈(ClO₄)₄ with 2,2′:6′,2′′-terpyridine (terpy) under non-aqueous conditions. At room temperature in acetonitrile, the combination of the U(IV) starting material with terpy resulted in a mixture containing [UO₂(DMSO)₂terpy][ClO₄]₂·MeCN, while increasing the water content led to the hydrolysis products [(UO₂(DMSO)terpy)₂(μ₂–O)][ClO₄]₂ and [(UO₂terpy)₂(μ₂–OH)₂][ClO₄]₂·MeCN·H₂O. Performing the reaction at slightly elevated temperature with no added water led to the formation of [UO₂sexipyridine][ClO₄]₂·MeCN. This new uranyl complex contains the hexadentate ligand 2,2′:6′,2′′:6′′,2′′:6′′′,2′′′′:6′′′′,2′′′′′-sexipyridine, which formed in situ from the tetravalent uranium starting material, where photoexcited uranyl or in situ generated peroxide could have induced C–C coupling. Analysis of bonding in the dimeric uranyl species via quantum chemical methods revealed a small increase in covalency of the bridging oxo unit and a slightly greater stability, compared to the bridging hydroxo compound, which causes a significant shift uranyl symmetric stretch in the Raman spectrum. Structural, spectroscopic, and computational comparisons are made across the series of compounds, providing insight into the bonding and reactivity of uranium in non-aqueous media.
SN - 0020-1669
SN - 1520-510X
ER -