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Six-nitrogen macrocyclic complexes of the dioxouranium(VI) and praseodymium(III) ions

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00317a011· OSTI ID:6950381
 [1];  [2]; ; ;  [3]
  1. Institute of Chemistry and Technology of Radioelements, Padova (Italy)
  2. Univ. of Milano (Italy)
  3. Virginia Commonwealth Univ., Richmond (USA)

The Schiff-base condensation of 2,6-diacetylpyridine and 1,2-diaminobenzene in the presence of uranyl salts produced complexes of the general formula (UP{sub 2}(C{sub 30}H{sub 26}N{sub 6}))X{sub 2}, with X = ClO{sub 4}{sup {minus}}, NO{sub 3}{sup {minus}}, and CH{sub 3}COO{sup {minus}}. A related complex, (Pr(NO{sub 3}){sub 2}(CH{sub 3}OH)(C{sub 30}H{sub 26}N{sub 6}))(ClO{sub 4}){center dot}0.5CH{sub 3}OH{center dot}0.5H{sub 2}O, was obtained from a similar metal-templated reaction followed by partial anion metathesis. The Pr(III) complex crystallized in the monoclinic space group P2{sub 1}/c with Z = 4 in a cell having a = 20.198 (3) {angstrom}, b = 14.208 (2) {angstrom}, c = 12.727 (2) {angstrom}, and {beta} = 104.25 (4){degree}. In this complex the Pr(III) ion was 11-coordinated, being linked to the six nitrogen atoms of an 18-membered macrocyclic ligand, to two bidentate nitrates situated on opposite sides of the macrocycle, and to one molecule of methanol. A noncoordinated ClO{sub 4}{sup {minus}} ion balanced the cationic charge of the complex cation; clathrated water and methanol were also present. The macrocyclic cations existing in these uranyl and praseodynium(III) complexes retained their identity in solution and were moderately inert to metal release in the present of acids or bases. 15 refs., 3 figs., 5 tabs.

OSTI ID:
6950381
Journal Information:
Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:18; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English