Journal
INORGANIC CHEMISTRY
Volume 46, Issue 12, Pages 4868-4875Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic062031m
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- Engineering and Physical Sciences Research Council [GR/S95169/01] Funding Source: researchfish
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Phosphinimine ligands (Cy3PNH) readily react with UO2Cl2(THF)(3) (THF = tetrahydrofuran) to give UO2Cl2(Cy3PNH)(2), which contains strong U-N interactions and exists as cis and trans isomers in the solid and solution state. Solution NMR experiments and computational analysis both support the trans form as the major isomer in solution, although the cis isomer becomes more stabilized with an increase in the dielectric constant of the solvent. Mayer bond orders, energy decomposition analysis, and examination of the molecular orbitals and total electron densities support a more covalent bonding interaction in the U-NHPCy3 bond compared with the analogous bond of the related U-OPCy3 compounds.
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