A Structural and Theoretical Investigation of Equatorial cis and trans Uranyl Phosphinimine and Uranyl Phosphine Oxide Complexes UO 2 Cl 2 (Cy 3 PNH) 2 and UO 2 Cl 2 (Cy 3 PO) 2
2007; American Chemical Society; Volume: 46; Issue: 12 Linguagem: Inglês
10.1021/ic062031m
ISSN1520-510X
AutoresL.J.L. Haller, Nikolas Kaltsoyannis, Mark J. Sarsfield, Iain May, S.M. Cornet, Michael P. Redmond, Madeleine Helliwell,
Tópico(s)Chemical Synthesis and Characterization
ResumoPhosphinimine 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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