Amide complexes of uranium tetrahalides and uranyl chloride

Abstract
Uranium tetrachloride and tetrabromide form 1 : 2 complexes with amides of the type R1·CO·NR2R3 when R1 or R2 and R3 are bulky branched chains (R1= Cme3, Me2CHCH2, or Me2CH with R2= R3= Me, and R1= Me with R2= R3= Pri) but form 1 : 4 complexes when R1= Me, R2= H, and R3= Et or Pri. The corresponding uranyl chloride complexes are all of composition UO2Cl2,2L except where L is CH3CONHEt, when a 1 :3 complex is obtained, I.r. spectroscopic results are reported for these, and some analogous thorium tetrachloride complexes. Studies of the u.v.–visible spectra of the complexes UX4,4L indicate that 1 :2 complexes are formed first in the reaction of the tetrahalide with the ligand and that the 1 :4 complexes react with halide ion in non-aqueous solvents to form octahedral anions [UX5L] and [UX6]2–.

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