The direct electrochemical synthesis of some thorium(IV) nitrate complexes

The electrochemical oxidation of thorium in either nitric acid/tri-n-butyl phosphate (TBP) or dinitrogen tetroxide/ethyl acetate/acetonitrile media gives rise to non-aqueous solutions of thorium(IV) nitrate species. The only neutral adduct which could be obtained from HNO 3 /TBP solution was Th(NO 3 ) 4• 8dmso (dmso = dimethylsulphoxide). Salts of [Th(NO 3 ) 6 ] 2− with Et 4 N + , [(bpyH) 3 NO 3 ] 2+ , and [(phenH) 3 NO 3 ] 2+ (bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) were also prepared by this route. Solutions in N 2 O 4 /EtOAc/CH 3 CN yield Th(NO 3 ) 4 , and neutral adducts with dmso, bpy, phen, Ph 3 PO, and pyridine-N-oxide.