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Syntheses and Crystal Structures of Potassium–Lanthanoid(III) Complexes with the 1,2‐Benzenedisulfonate Ligand
Author(s) -
Deacon Glen B.,
Gitlits Alex,
Zelesny Gerd,
Stellfeldt Dirk,
Meyer Gerd
Publication year - 1999
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/(sici)1521-3749(199905)625:5<764::aid-zaac764>3.0.co;2-h
Subject(s) - sulfonate , chemistry , lanthanide , crystal structure , potassium , crystallography , molecule , isostructural , inorganic chemistry , ligand (biochemistry) , ion , oxygen , medicinal chemistry , stereochemistry , sodium , organic chemistry , receptor , biochemistry
The complexes [K(H 2 O) 2 LnL 2 ] (Ln = La or Nd; L = 1,2‐benzenedisulfonate) and [K(H 2 O)Yb(H 2 O) 4 L 2 ] were initially isolated fortuitously from attempts to prepare the corresponding Ln 2 L 3 complexes from Ln 2 O 3 and H 2 L in water. Indeed the bulk products from these reactions have the composition Ln 2 L 3 . Subsequently, deliberate syntheses by reacting equimolar amounts of Ln 2 L 3 with K 2 L in water gave the complexes in good yield. X‐ray crystal structures of [K(H 2 O) 2 LnL 2 ] (Ln = La or Nd) showed the complexes to be isostructural with a two dimensional polymeric network structure in which LnL 2 units are linked into chains crosslinked by potassium ions. Each Ln is nine coordinate with solely sulfonate oxygen donor atoms. Between adjacent lanthanoid ions there are three different types of sulfonate bridges and two examples of each. Most noteworthy is highly unsymmetrical bridging through μ‐η 2 ‐sulfonate oxygen atoms. Consequently, one Ln–O bond is ca. 0.5 Å longer than the other eight. Potassium is nine‐coordinate with seven sulfonate oxygen atoms and two aqua ligands, and surprisingly is much longer than . Pairs of potassium ions are linked by two μ‐η 2 ‐sulfonate oxygen atoms, which are unsymmetrically bridging. The structure of [K(H 2 O)Yb(H 2 O) 4 L 2 ] comprises discrete tetranuclear units containing two independent ytterbium ions, each coordinated by four water molecules and two chelating (via seven membered rings) disulfonate ligands, and two potassium ions, each coordinated by six sulfonate oxygen atoms and a water molecule. For each potassium, four of the coordinated sulfonate oxygen atoms are from sulfonate ligands bonded to one ytterbium atom and two from sulfonate ligands attached to the other ytterbium atom. In contrast to the Nd and La complexes, is shorter than .