Specific sequestering agents for the actinides. 9. Synthesis of metal complexes of 1-hydroxy-2-pyridinone and the crystal structure of tetrakis(1-oxy-2-pyridinone)aquathorium(IV) dihydrate

Abstract

Die Komplexe (I) werden durch l :4‐molare Umsetzung von ThCl4‐8H3O, U(′I4, (NH4)4[Ce(SO4)4] oder Zr(NO3)4 mit dem Na‐Salz des Titelliganden in wäßriger Lösung gebildet und nach dem Umkristallisieren isoliert.

Synthesis and Structural Study of Tetravalent (Zr4+, Hf4+, Ce4+, Th4+, U4+) Metal Complexes with Cyclic Hydroxamic Acids

“…It is worth noting that the evolution of the M–O C and M–O N bond lengths perfectly reflects the variation in ionic radii of these eight‐coordinate M 4+ ions (Table 2), which shows a linear dependence within the [M( 1 ) 4 ] series (Figure S23 in the Supporting Information) 28. The same trend was also observed for 1,2‐HOPO – complexes with 4f and 5f elements, such as in [M( 5 ) 4 ] (M 4+ = Ce 4+ , Pu 4+ )10e and in the nine‐coordinate [Th( 5 ) 4 (H 2 O)] complex 10a,10b…”

“…However, the same authors found a diversity of coordination stereochemistries when the same ligand was crystallized with either thorium or plutonium. Indeed, the former complexes are nine‐coordinate with a [Th( 5 ) 4 (L)] formula and resembling a D 3 h tricapped trigonal prism for L = H 2 O10a or a distorted monocapped square antiprism for L = MeOH 10b. In turn, [Pu( 5 ) 4 ] adopts an intermediate DD–BTP geometry 10e.…”

Lauriston S. Taylor Lecture: The Quest for Therapeutic Actinide Chelators

“…3), and they were expected to bind Ln(III), An(III), and An(IV) stably over the range of physiological pH (Scarrow 1985;Scarrow et al 1985a). Crystals of Th(IV)-(1,2-HOPO) 4 could be prepared in neutral aqueous solution (Riley et al 1983), in contrast to crystals of the tetrakis Th(IV) complexes with hydroxamic acids (Smith and Raymond 1981) or catechol (Sofen et al 1978), which could only be obtained under alkaline conditions. Ligands containing 1,2-HOPO.…”

Bis(2-oxopyridinatoN-oxide-κ2O,O′)copper(II)

“…Many metal complexes with pyridine N-oxide and its derivatives have been reported in the past few decades as a result of their interesting coordination chemistry (Karayannis et al, 1973(Karayannis et al, , 1976Landers & Phillips, 1982;Casellato et al, 1983;Riley et al, 1983;Scarrow et al, 1985;Lobana & Singh, 1995). However, metal complexes with chelating derivatives of pyridine N-oxide with donor atoms in the 2-position, such as 2-hydroxypyridine N-oxide (opo) (Hubbard et al, 1979;Landers & Phillips, 1981), have been less well studied and little work has been carried out on the X-ray crystal structures of complexes of this class (Casellato et al, 1983;Riley et al, 1983). Here, we report the synthesis and structure of the square-planar title compound, [Cu(opo) 2 ], (I).…”