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Oxalato-Bridged Dinuclear Copper(II) Complexes of N-Alkylated Derivatives of 1,4,7-Triazacyclononane: Synthesis, X-ray Crystal Structures and Magnetic Properties

✍ Scribed by Matthew J. Belousoff; Bim Graham; Boujemaa Moubaraki; Keith S. Murray; Leone Spiccia

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
210 KB
Volume
2006
Category
Article
ISSN
1434-1948

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✦ Synopsis

Abstract

The synthesis, X‐ray crystal structure and magnetic properties of two oxalato‐bridged dinuclear Cu^II^ complexes, L‐Cu(μ‐ox)Cu‐L~2~, where ox = oxalate and L = 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me~3~tacn) or 1‐benzyl‐4,7‐dimethyl‐1,4,7‐triazacyclononane (BzMe~2~tacn) are reported, as well as the X‐ray crystal structure of the mononuclear complex, Cu(Me~3~tacn)(OH~2~)~2~~2~, which features an extended H‐bonding network between the ligand and the perchlorate counterions. The crystal structures of the dinuclear complexes both feature a centrosymmetric complex cation in which the two copper centres exist in a distorted square‐pyramidal geometry, with each end capped by a facially coordinated “tacn” unit, and are bridged by an oxalate anion. Variable‐temperature magnetic susceptibility measurements revealed strong antiferromagnetic interactions between the Cu^II^ centres, with 2__J__ values of ca. –300 cm^–1^, even though the Cu···Cu separation is very long, viz. 5.18 Å (BzMe~2~tacn) and 5.47 Å (Me~3~tacn). The separation for the Me~3~tacn complex is the longest separation reported for this type of Cu^II^ complex. No pattern could be detected between the J values and structural features for 21 oxalato‐bridged complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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