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Systematic structural coordination chemistry of p-tert-Butyltetrathiacalixarene: further complexes of Transition-Metal Ions
In extension of earlier work on complexes of p-tert-butyltetrathiacalixarene, LH4, with late transition-metal MII species, we report studies of complexes modelled on the basis of single-crystal X-ray studies as derivatives of VV, WVI, MnII, FeIII, NiII, CuII and PdII, the last as a trio of heteronuclear species also involving CaII. In complexes [VO(OH)(LH2)·2.5dmf·2H2O] (×2) (1), Cl2W(L)·3.5C6H6 (2) and [Mn(LH2)·3.5CH2Cl2] (×2) (3) included dmf is found only in the partially deprotonated calixarene cavities of 1 and 3. In oligonuclear OFe3(HCO2)(LH)2·2H2O·6dmf (4) and 2Cuac2·Cu2(L)·dmf·4.5CH2Cl2 (6) (ac = acetate) included dmf is found in both. NiII provides several species, including 5a, binuclear (Et3NH)Ni2(LH)(LH2)·2dmf·2Me2CO·H2O, 5b, a remarkable hexanuclear (binuclear + tetranuclear) aggregate, Ni6(L)(LH)2(LH2)·4MeCN·6H2O, and 5c, an even more remarkable Ni32 aggregate modelled as (centrosymmetric) Ni32(OH)40(L)6·8dmso·10dmf, in which there are two sets of nickel atoms, one disposed at the corners of a cube (Ni8), the other (Ni24) at the vertices of a cuboctahedron (the Ni8 vertices at the centres of the hexagonal faces); the hydroxy groups comprise two sets: one, (OH)24, disposed outside the spheroidal shell of nickel atoms, the other, (OH)16, disordered within, the thiacalixarene ligands L6 being disposed about the axes of the octahedron. Heteronuclear species have been found as CaII/PdII combinations CaPd2(LH)2·1.5CH2Cl2 (7a), CaPd(LH2)·3dmso·H2O·4.5MeCN (7b), Ca2Pd(LH)2·3.5dmso·1.5H2O·4MeCN (7c), all with included solvent.
Publication titleEuropean Journal of Inorganic Chemistry
Department/SchoolSchool of Natural Sciences
PublisherWiley-V C H Verlag Gmbh
Place of publicationPo Box 10 11 61, Weinheim, Germany, D-69451
Rights statement© 2010 Wiley-VCH Verlag 2106 GmbH & Co. KGaA, Weinheim