title: Toward equatorial planarity about uranyl: synthesis and structure of tridentate nitrogen-donor {UO2}2+ complexes.
abstract: The reaction of UO2Cl2·3THF with the tridentate nitrogen donor ligand 2,6-bis(2-benzimidazolyl)pyridine (H2BBP) in pyridine leads to the formation of three different complexes: [(UO2)(H2BBP)Cl2] (1), [(UO)2(HBBP)(Py)Cl] (2), and [(UO2)(BBP)(Py)2] (3) after successive deprotonation of H2BBP with a strong base. Crystallographic determination of 1-3 reveals that increased charge through ligand deprotonation and displacement of chloride leads to equatorial planarity about uranyl as well as a more compact overall coordination geometry. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra of 1-3 at the U-4d edges have been recorded using a soft X-ray Scanning Transmission X-ray Microscope (STXM) and reveal the uranium 4d5/2 and 4d3/2 transitions at energies associated with uranium in the hexavalent oxidation state. First-principles Density Functional Theory (DFT) electronic structure calculations for the complexes have been performed to determine and validate the coordination characteristics, which correspond well to the experimental results.
authors: Chemical Sciences Division, The Glenn T. Seaborg Center, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
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