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Compounds of copper(II) and nickel(II) with 6,6,13,13-tetracarboxy-(andE-6,13-dicarboxy-) substituted 1,4,8,11-tetrazacyclotetradecanes, and carbomethoxy- and carbethoxy- derivatives. Structures of two isomericE-6,13-dicarboxy- (and anE-6,13-dicarbomethoxy-)1,4,8,11-tetrazacyclotetradecane copper(II) perchlorates

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Summary

Bis(ethanediamine) complex cations of CuII and NiII react with formaldehyde and diethyl- (or dimethyl-) malonate to form complexes of 6,6,13,13-tetracarbomethoxy- (or carbethoxy-) 1,4,8,11-tetraazacyclotetradecane macrocycles. These hydrolyse in base to give tetracarboxy-substituted cations, which decarboxylate in acid toE-6,13-dicarboxy-substituted cations. For CuII, salts of this cation were isolated in a metastable form, which converted in base to the stable form. These isomeric dicarboxy-substituted cations esterified to form perchlorate salts of the isomeric CuII compounds of theE-dicarbomethoxy-substituted cations. The structures of the perchlorate salts of the two isomers of the 6,13-dicarboxy-and the metastable isomer of the 6,13-dicarbomethoxy-substituted macrocycles were determined by x-ray diffraction. All have the macrocycles in squareplanar coordination in theRSSR configuration, with perchlorate oxygen atoms weakly coordinated axially. The metastable dicarboxy- and dicarbomethoxy compounds have the substituent groups axially oriented (1α, 4β, 6β, 8β, 11α, 13α) while the stable dicarboxy-compound has the substituents equatorially oriented (1α, 4β, 6β, 8β, 11α, 13α). The compounds are demetallated very slowly in acid, allowing the isolation of freeE-6,13-dicarboxy-1,4,8,11-tetrazacyclotetradecane.

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  1. Li Xin

    Present address: Chemistry Department, Harbin Teachers University, Harbin, Chinese Peoples Republic

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  1. Chemistry Department, Victoria University of Wellington, Box 600, Wellington, New Zealand

    Li Xin, Neil F. Curtis & David C. Weatherburn

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  2. Neil F. Curtis
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Xin, L., Curtis, N.F. & Weatherburn, D.C. Compounds of copper(II) and nickel(II) with 6,6,13,13-tetracarboxy-(andE-6,13-dicarboxy-) substituted 1,4,8,11-tetrazacyclotetradecanes, and carbomethoxy- and carbethoxy- derivatives. Structures of two isomericE-6,13-dicarboxy- (and anE-6,13-dicarbomethoxy-)1,4,8,11-tetrazacyclotetradecane copper(II) perchlorates. Transition Met. Chem. 17, 147–154 (1992). https://doi.org/10.1007/BF02910808

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