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Thiosemicarbazone Complexes of Uranium
Author(s) -
Abram Ulrich,
Schulz Lang Ernesto,
Bonfada Elida
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200208)628:8<1873::aid-zaac1873>3.0.co;2-i
Subject(s) - chemistry , deprotonation , semicarbazone , protonation , dimer , triethylamine , uranyl , metal , crystallography , methanol , actinide , crystal structure , thorium , medicinal chemistry , stereochemistry , inorganic chemistry , uranium , ion , organic chemistry , materials science , metallurgy
Acetylpyridine thiosemicarbazone, HAPTSC ( 1 ), reacts with uranyl nitrate in MeOH under formation of (H 2 APTSC) 2 —[UO 2 (NO 3 ) 2 (μ‐OH)] 2 ( 2 ) or [ UO 2 (APTSC)(MeOH)(MeO)] 2 ( 3 ) depending on the experimental conditions applied. Protonation of 1 and precipitation of the [UO 2 (NO 3 ) 2 (μ‐OH)] 2 2— dianion as acetylpyridinium thiosemicarbazone salt is observed when the reaction is performed without the addition of a base. The metal atoms are situated in the centres of distorted hexagonal bipyramids. The U—U distance is 3.892(1)Å. Addition of triethylamine results in deprotonation of HAPTSC and the formation of 3 which is an unusual dimer with four methanol/methanolato ligands of two metal sites sharing two protons. The U—U distance in this dimer is 5.313(1)Å. (Bu 4 N)[UO 2 —(APTSC)Cl 2 ] ( 4 ) is obtained when (Bu 4 N) 2 [UO 2 Cl 4 ] is used as precursor. The uranium atoms in 3 and 4 are seven co‐ordinate. Their co‐ordination polyhedra can best be described as pentagonal bipyramids. Compounds 3 and 4 represent the first examples of thiosemicarbazone complexes with actinide elements which haven been studied by X‐ray analysis.