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Sobolev, Alexandre
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Topics
Publications (11/11 displayed)
- 2023Structure of Bis(Lidocaine) Tetrachloridoferrate(III) Chloride
- 2023Inert Transition Metal Ion Complexes in Organic Synthesiscitations
- 2021Uranyl complexes of p-t-butylcalix[8]arene as H-bond acceptors—subtle effects of the donorscitations
- 2021Crystal structure of hexakis(N, N-dimethylformamide-κ O)iron(III) μ-chlorido-bis(trichloridocadmium)citations
- 2020Structure Reassignment of Echinosulfone A and the Echinosulfonic Acids A-D Supported by Single-Crystal X-ray Diffraction and Density Functional Theory Analysiscitations
- 2020Structural Systematics of Lanthanide(iii) Picrate Solvatescitations
- 2020Synthesis and Structures of Bis- A nd Tris-(triphenylarsine)gold(i) Iodides
- 2019Crystal structures of an imidazo[1,5-a]pyridinium-based ligand and its (C13H12N3)(2)[CdI4] hybrid saltcitations
- 2008Nanoporous materials based on heteroleptic bilayers built up from bisphosphonium, p-sulfonatocalix[4]arene ionscitations
- 2007Variable temperature Hirshfeld surface analysis of interdigitated calix[6]arene bearing O-alkyl C18 linear chainscitations
- 2003Cation movement and phase transitions in KTP isostructures; X-ray study of sodium-doped KTP at 10.5 Kcitations
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article
Structural Systematics of Lanthanide(iii) Picrate Solvates
Abstract
<p>Crystalline products of the reactions of lanthanide picrates, Ln(pic)<sub>3</sub> (pic = 2,4,6-trinitrophenoxide), with hexamethylphosphoramide (hmpa) and octamethylpyrophosphoramide (ompa) have been characterised by single-crystal X-ray diffraction studies. With hmpa and lighter lanthanides (La, Sm, Eu), isomorphous species (monoclinic, P2<sub>1</sub>/c, Z 4) of stoichiometry [Ln(pic)<sub>3</sub>(hmpa)<sub>3</sub>]·0.5H<sub>2</sub>O, have been defined where the molecular units in the lattice contain 9-coordinate Ln with tricapped trigonal-prismatic coordination geometry. The picrate ligands are bidentate through phenoxide-O and 2-nitro-O, with the latter occupying the capping positions, while the hmpa ligands are singly O-bound to one trigonal face. Heavier lanthanides (Gd, Lu) and Y have been found to give isomorphous (monoclinic, P2<sub>1</sub>/n, Z 4) species of stoichiometry [Ln(pic)<sub>3</sub>(hmpa)<sub>2</sub>], with 8-coordinate Ln of an irregular geometry best considered as close to that of a bicapped trigonal-prism. The picrate ligands chelate in the same manner as in the lighter Ln complexes but with one spanning a trigonal edge, and the hmpa-O donors occuping two apices of the other trigonal face. The ligand ompa has been found to act as a bidentate chelate in all isolated species, displacing one picrate from the metal ion coordination sphere to give ionic complexes. For La, Nd, and Gd, isomorphous (monoclinic, P2<sub>1</sub>/n, Z 4) complexes of stoichiometry [Ln(pic)<sub>2</sub>(ompa)<sub>2</sub>(OH<sub>2</sub>)](pic)·0.5H<sub>2</sub>O containing 9-coordinate, tricapped trigonal-prismatic Ln with a single aqua ligand have been defined, while for Er, Yb, Lu, and Y, both the coordinated and lattice water molecules are lost in isomorphous (monoclininc, P2<sub>1</sub>/c, Z 8) 8-coordinate, square-antiprismatic species of stoichiometry [Ln(pic)<sub>2</sub>(ompa)<sub>2</sub>](pic). For Er, further polymorphs, one monoclinic, P2<sub>1</sub>/c, and the other triclinic, CH19251-IE1.gif, have also been characterised.</p>