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Systematic structural coordination chemistry of p-tert-Butyltetrathiacalix[4]arene: further complexes of Transition-Metal Ions


Bilyk, A and Dunlop, JW and Fuller, RO and Hall, AK and Harrowfield, JM and Hosseini, MW and Koutsantonis, GA and Murray, IW and Skelton, BW and Stamps, RL and White, AH, Systematic structural coordination chemistry of p-tert-Butyltetrathiacalix[4]arene: further complexes of Transition-Metal Ions, European Journal of Inorganic Chemistry, 2010, (14) pp. 2106-2126. ISSN 1434-1948 (2010) [Refereed Article]

Copyright Statement

2010 Wiley-VCH Verlag 2106 GmbH & Co. KGaA, Weinheim

DOI: doi:10.1002/ejic.200901071


In extension of earlier work on complexes of p-tert-butyltetrathiacalix[4]arene, 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)2.5dmf2H2O] (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)22H2O6dmf (4) and 2Cuac2Cu2(L)dmf4.5CH2Cl2 (6) (ac = acetate) included dmf is found in both. NiII provides several species, including 5a, binuclear (Et3NH)Ni2(LH)(LH2)2dmf2Me2COH2O, 5b, a remarkable hexanuclear (binuclear + tetranuclear) aggregate, Ni6(L)(LH)2(LH2)4MeCN6H2O, and 5c, an even more remarkable Ni32 aggregate modelled as (centrosymmetric) Ni32(OH)40(L)68dmso10dmf, 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)21.5CH2Cl2 (7a), CaPd(LH2)3dmsoH2O4.5MeCN (7b), Ca2Pd(LH)23.5dmso1.5H2O4MeCN (7c), all with included solvent.

Item Details

Item Type:Refereed Article
Keywords:calixarenes, transition metals, solvent inclusion, solid-state structures
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Fuller, RO (Dr Rebecca Fuller)
ID Code:153931
Year Published:2010
Web of Science® Times Cited:81
Deposited By:Chemistry
Deposited On:2022-10-17
Last Modified:2022-11-03

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