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Structural Systematics of Lanthanide(III) Picrate Solvates: Neutral, Mononuclear Ln(pic)3(dimethylsulfoxide)3 Arrays

Abstract : Adducts of dimethylsulfoxide, dmso = Me2SO, with lanthanide(iii) picrates (picrate = 2,4,6-trinitrophenoxide, pic) of stoichiometry Ln(pic)3·3dmso have been prepared and characterised by single-crystal X-ray structure determinations as discrete, neutral, mononuclear molecular species. Such complexes have been obtained across the gamut of Ln, specifically for Ln = La, Pr, Nd, Sm, Gd, Dy, Yb, Lu, and Y, presumably also accessible for other intermediate members, the series being isomorphous (monoclinic, C2/c, Z = 8); a second triclinic P form has also been identified for Ln = La, Pr. In both forms, the metal atom coordination environments are nine-coordinate, tricapped trigonal prismatic, [Ln(dmso-O)3(pic-O,O′)3], two of the three unidentate ligands lying in one of the trigonal planes and one in the other (an isomer we have termed meridional, mer). A hydrated form of Ln(pic)3·2dmso·H2O stoichiometry has also been defined for Ln = Sm, Gd, Lu, the metal atom environment again nine-coordinate, [Ln(dmso-O)2(H2O)(pic-O,O′)3], but now fac, with the three unidentate ligands occupying one triangular face of the tricapped trigonal prism and involved in a centrosymmetric H-bonding array with the three similar ligands of an adjacent complex; the three capping atoms are nitro-oxygen atoms, the phenoxy-O triad occupying the other face.
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https://hal-cea.archives-ouvertes.fr/cea-02908984
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Submitted on : Wednesday, July 29, 2020 - 5:05:08 PM
Last modification on : Thursday, July 30, 2020 - 4:11:24 AM

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Zouhair Asfari, Eric Chan, Jack Harrowfield, Brian Skelton, Alexandre Sobolev, et al.. Structural Systematics of Lanthanide(III) Picrate Solvates: Neutral, Mononuclear Ln(pic)3(dimethylsulfoxide)3 Arrays. Australian Journal of Chemistry, CSIRO Publishing, 2019, 73 (6), pp.447. ⟨10.1071/CH19169⟩. ⟨cea-02908984⟩

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