Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 35, Pages 13185-13192Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja406610r
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Funding
- Research Corporation for Science Advancement
- University of Pennsylvania
- U.S. National Science Foundation [OCI-1053575]
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Thermally stable uranium(VI)-methyl and -acetylide complexes: (UOR)-O-VI[N(SiMe3)(2)](3) R = -CH3, -C=CPh were prepared in which coordination of the hydrocarbyl group is directed trans to the uranium-oxo multiple bond. The stability of the uranium-carbon bond is attributed to an inverse trans influence. The hydrocarbyl complexes show greater ITI stabilization than that of structurally related (UOX)-O-VI[N(SiMe3)(2)](3) (X = F-, Cl-, Br-) complexes, demonstrated both experimentally and computationally. An inverse trans influence ligand series is presented, developed from a union of theoretical and experimental results and based on correlations between the extent of cis-destabilization, the complexes stabilities toward electrochemical reduction, the thermodynamic driving forces for U=O bond formation, and the calculated destabilization of axial sigma and pi* antibonding interactions.
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