The Crystal and Molecular Structure of Scandium(III), Yttrium(III), and Some Lanthanoid(III) p-Toluenesulfonates, [Sc(C7H7SO3)2(H2O)4](C7H7SO3)·2H2O and [M(C7H7SO3)2(H2O)6](C7H7SO3)·3H2O (M=Y, Sm, Gd, Dy, Ho, Er, Yb); and Yttrium(III) and Dysprosium(III) 2-Naphthalenesulfonates, [M(C10H7SO3)2(H2O)6](C10H7SO3)·3H2O (M=Y, Dy)

Abstract

Scandium(III) p-toluenesulfonate hexahydrate, as well as the isomorphous yttrium(III) and six lanthanoid(III) (Sm, Gd, Dy, Ho, Er, and Yb) p-toluenesulfonate enneahydrates, were synthesized and their structures were determined by the single-crystal X-ray diffraction technique. The scandium salt was monoclinic with the space group P21⁄a, Z=4 (the cell constants were a=23.672(16), b=15.792(6), c=7.7543(12) Å, β=92.86(3)°, and the final R value was 0.059). The central metal atom is hexa-coordinated, being in an octahedral geometry, in which two unidentate sulfonate oxygen atoms (in cis-configuration) and four water oxygen atoms are ligated. The latter seven salts were also monoclinic with a space group of P21⁄n, and Z=4 (the cell constants of the holmium salt, for example, were a=25.058(19), b=7.476(2), c=17.802(10) Å, β=98.80(8)°, and its final R value was 0.039). The central metal atom of these complexes are octa-coordinated, being in a square-antiprism geometry in which two unidentate sulfonate and six water oxygen atoms are ligated. In both types of complexes, no ligand bridgings were found, and one in three sulfonate ions was not coordinated to the metal atom. In the respective lanthanoid(III) complexes, M–O(sulfonato) bonds are shorter than the M–O(water) ones. The corresponding M–O bonds of the respective complexes decrease, almost proportional to the sum of the Shannon’s ionic radii of the metal and oxygen, with the metal atomic numbers. Each M–O bond length of the yttrium(III) p-toluenesulfonate and 2-naphthalenesulfonate had the value expected from the corresponding bond lengths of the series of the respective isomorphous lanthanoid(III) salts, referring to its metal ionic radius.

Structure of ammonium p-toluenesulfonate

“…(1967) Introduction. p-Toluenesulfonate salts have been extensively utilized as leaving groups in organic syntheses and as anions in many inorganic reactions (Ohki, Suzuki, Takeuchi & Ouchi, 1988;Bernhard, Burgi, Hauser, Lehmann & Ludi, 1982). The isolation of the title complex was a result of our efforts directed to the synthesis and modification of crown ethers with improved heavy-metal extraction properties.…”

Lanthanide(III) Tosylates as New Acylation Catalysts

“…[22] Since the coordination number of the trivalent lanthanide ion is commonly eight or nine, it has been suggested that the coordination mode of the sulfonate anions changes upon removal of the hydrated water molecules from the crystal, so that they act as multidentate ligands forming more metal-oxygen bonds in order to replace the removed water oxygen atoms in the first coordination sphere of the lanthanide(iii) ion. The elemental analysis results of lanthanide(iii) tosylate catalysts (see Experimental Section) indicated that some water of crystallization is lost upon drying of the crystalline solid at 50°C in vacuo, but that the complexes still contain one to three molecules of water.…”

“…[22,26] For example, in the La(TOS) 3 ·9 H 2 O complex, nine water molecules occupy the first coordination sphere and the tosylate counterions are merely spectator ions located in the second coordination sphere. [26] In contrast, the structure of Yb(TOS) 3 is markedly different: the coordination environment around the ytterbium(iii) is occupied by two oxygen atoms from the sulfonate group of TOS and six oxygen atoms from water molecules.…”

Lanthanide(III) Nitrobenzenesulfonates as New Nitration Catalysts: The Role of the Metal and of the Counterion in the Catalytic Efficiency

“…55°C. [16] As the coordination number of the lanthanides is always high (commonly 8 or 9), it has been proposed that upon removal of hydrated water molecules from the crystal, the sulfonate anions move and act as multidentate ligands forming more metal-oxygen bonds in place of the removed water oxygen atoms. The elemental analysis results of lanthanide() complexes with nitrosulfonic acids (Exp.…”

“…In contrary, the ytterbium() tosylate complex has a structure very similar to the structure of Yb(m-NBSA) 3 in which two ligands are directly bound to ytterbium(). [16] The analogy between the structures of the lanthanide() nitrobenzenesulfonate and lanthanide() tosylate complexes is not surprising, if one takes into account the similarities of the nitrobenzenesulfonate and tosylate structures and their similar pK a values.…”