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Issue 22, 1992

Cascade complexes of an octaaza cryptand: co-ordinated azide with linear M–NNN–M geometry

Abstract

The octaamino cryptand, L2, obtained by tetrahydroborate reduction of the [2 + 3] condensation product of tris(2-ethylamino)amine with terephthalaldehyde, acts as a host for pairs of protons or first-series transition-metal cations. An X-ray crystallographic structure determination of [H4L2]4+ reveals a pair of protons held at opposite ends of the molecule by strong intramolecular hydrogen bonding of each proton to two of the amino nitrogen atoms. Pairs of transition-metal cations co-ordinated to the amino N-donors accommodate mono- and tri-atomic bridging ligands, such as OH or imidazolate, generating weak to moderate antiferromagnetic interaction. Dicopper(II)µ-azido complexes have been prepared where the combination of a large zero-field splitting in the ESR spectrum and a near Curie-law dependence of magnetic susceptibility on temperature seems to suggest a triplet ground state. Together with other unusual spectroscopic properties of the bridging azide group, this is believed to derive from a near-linear alignment of the M–NNN–M assembly.

Article information


J. Chem. Soc., Dalton Trans., 1992, 3235-3242
Article type
Paper

Cascade complexes of an octaaza cryptand: co-ordinated azide with linear M–NNN–M geometry

M. G. B. Drew, J. Hunter, D. J. Marrs, J. Nelson and C. Harding, J. Chem. Soc., Dalton Trans., 1992, 3235 DOI: 10.1039/DT9920003235

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