The NHR2/CO2 system as a metal ion extraction reagent from aqueous solution into hydrocarbons:: copper(II) and zinc(II)

A substantially quantitative transfer of copper(II) or zinc(II) salts from aqueous solution into a hydrocarbon (heptane or toluene) promptly occurs under carbon dioxide in the presence of a dialkylamine (NHR2, R = Bu, Bz). Recovery of the metal complexes from the organic phase affords copper dialkylcarbamates of the formula Cu(O2CNR2)(2)(NHR2)(2) or mu-oxo tetranuclear zinc carbamato complexes, Zn-4(mu(4)-O)(O2CNR2)(6), respectively, in high yield and purity. An X-ray diffraction study on a single crystal of Cu(O(2)CNBz(2))(2)(NHBz(2))(2) 1 has shown the compound to be mononuclear with tetracoordinated copper in an almost perfect square-planar geometry. The zinc derivative has the well-established oxo-centred tetranuclear structure (R = Bu, 2). (C) 2002 Elsevier Science B.V. All rights reserved.