Related Experiment Video
Updated: Jun 23, 2026
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Reactions of U(DMSO)8(ClO4)4 with Terpyridine Yield Dimeric Hydrolysis Products and Induce C-C Coupling
Emily R Mikeska1, Richard E Wilson1, Valérie Vallet2
1Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
Abstract:
Reactions have been carried out using UIV(DMSO)8(ClO4)4 with 2,2':6',2″-terpyridine (terpy) under nonaqueous 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 in the 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 nonaqueous media.
Related Concept Videos
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Cycloaddition Reactions: MO Requirements for Thermal Activation
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

