Combined experimental and theoretical studies of some uranium(VI) complexes derived from imidazole-based carbenes.

A series of bidentate, viz., 1,1'-(1,2-ethylene)-3,3'-dimethyldiimidazoline-2,2'-diylidene (L1), 1-methyl-3-(2-pyridylmethyl)-imidazoline-2-ylidene (L2) and tridentate, viz., 1,3-bis(2-pyridyl)-imidazoline-2-ylidene (L3) ligands have been obtained from their corresponding imidazolium salts through deprotonation reactions. Treatment of UO2Cl2(THF)3 with one equivalent L3 produces air-stable U(VI)-carbene complex 3, characterized by elemental analysis, FTIR, NMR spectroscopy as well as extended X-ray absorption fine structure (EXAFS) analysis. EXAFS result indicates that the ligand is bonded through one C and two N-atoms to the uranium atom. Attempts to synthesize uranyl complexes derived from L1 and L2 were also successful but these complexes are decomposed quickly within one hour at room temperature. 3 produces pure UO2 powder when heated under an argon atmosphere from room temperature to 600 °C with constant heating rate of 5 °C/min. The solid-state UV–Vis spectrum of the compound shows absorption peaks at 332 and 450 nm. The excitation spectrum of 3 (at λem = 520 nm) exhibits two almost symmetrical peaks at 273 and 368 nm. Density functional theory-based quantum mechanical calculations indicate that a partial covalent interaction exists between the carbene C and U while a weak non-covalent interaction exists between carbene N and U atoms. [ABSTRACT FROM AUTHOR]