Preparation of Mono- and Binuclear Complexes of Copper(II), Nickel(II), Cobalt(II), Iron(III), and Vanadyl(V) with 2,2' - Dyhydroxy-3,3'- Dyacetyl-5,5'-Dichlorodiphenylmethane.

The synthesis of mononuclear complexes M(HL)2.nS [M = copper(II), nickel (II) and cobalt(II), S = solvent] and M'(HL)2OH.nS [M' = iron(III) and vanadyl(V)] and of the binuclear complexes M2L2.nS [M = copper(II), nickel(II) and cobalt(II)] and Fe2L2(OH)2.H2O and (VO)2L2SO4.4H2O derived from 2,2'-dihydroxy-3,3'-diacetyl-5,5'-dichlorodiphenylmethane (H2L) is reported. Their coordination geometry is discussed on the basis of physico-chemical data. Magnetic measurements at room temperature suggest that no interactions between metal ions are present in the binuclear chelates. Iron(III) and vanadyl(V) complexes were used as catalysts for the oxidation of 3,5-di-t-butyl-1,2-dihydroxybenzene (3,5-DBTC). From the oxidative cleavage, 3,5-di-t-butyl-o-quinone (3,5-DTBQ), 3,5-di-t-butyl-1-oxacyclohepta-3,5-diene-2,7-dione (3,5-DTBODD), 3,5-di-t-butyl-5-carboxymethyl-2-furanone (3,5-DTBCF) and 4,6-di-t-butylpyrone-2-one (4,6-DTBP) were isolated and identified by mass, IR and H-1 NMR data. The title compound was reacted to give a hexaketone by application of the Wittig method. A polymeric Schiff base was obtained by reaction of the diacetyl derivative with ethylenediamine, also in the presence of nickel(II) perchlorate or boric acid

A Thermogravimetric, Single Crystal X-ray, and Spectroscopic Study of Several Iron (III) Halide Adducts with Crown Ethers

The interaction of iron(III) halides with 18-crown-6 or 15-crown-5 ethers has led to the isolation of several complexes, two of which, [FeCl3(H2O)2] (15-crown-5) and H(FeBr4) (15-crown-5)2(H2O)2, yielded crystals suitable for single crystal X-ray structural analysis. The chloro complex crystallizes in the monoclinic P21 (No. 4) space group with Z = 2, a = 8.574(1), b = 13.714(2), c = 8.223(1) A ̊, β = 107.9 (1)°. The crystals contain trigonal bipyramidal [FeCl3(H2O)2] moieties hydrogen bonded to a partially disordered 15-crown-5 ether to form a polymeric chain oriented along the crystallographic c-axis. The bromo complex crystallizes in the cubic Fd3 (No. 203) space group with Z = 8, a = 19.500(2) A ̊. The compound contains tetrahedral FeBr4- anions which have no bonding interaction with the 15-crown-5 ether, which simply acts as a dielectric medium to separate the anions. A study of the thermal decomposition of the compounds was performed by thermogravimetric analysis. IR and Mössbauer spectral measurements indicate that the decomposition products are water, acetaldehyde, dioxane, chlorine or bromine, carbon dioxide, carbon monoxide, and mixtures of hydrated iron(II) halides and iron oxides. © 1995