Brandt, Carsten D., Kitchen, Jonathan A., Beckmann, Udo, White, Nicholas G., Jameson, Geoffrey B. and Brooker, Sally (2007) Synthesis and structures of 3,5-disubstituted 1,2,4-triazole head units and incorporation of 3,5-dibenzoyl-1,2,4-triazolate into new [2 + 2] Schiff-base macrocyclic complexes. Supramolecular Chemistry, 19 (1-2), 17-27. (doi:10.1080/10610270600902340).
Abstract
The synthesis and characterization of sodium 3,5-diacetyl- 1,2,4- triazolate (4 (Me)) and sodium 3,5-dibenzoyl-1,2,4- triazolate (4 (Ph)), both of which can be used as head unit building blocks in Schiff-base reactions, are reported. The crystal structures of sodium 3,5-diacetyl-1,2,4- triazolate, as [4 (Me)(H2O)]infinity, and sodium 3,5-dibenzoyl-1,2,4- triazolate, as [4 (Ph)(CH3OH)(2] 2), have been determined. The former is a helical polymer whilst the latter is a methanol-bridged dimer. The lead(II) templated cyclization reaction of sodium 3,5-dibenzoyl-1,2,4-triazolate (4 (Ph)) with 1,3-diaminopropane or 1,4-diaminobutane, respectively, leads to the formation of two new [ 2 + 2] Schiff-base macrocycles as their lead(II) complexes, [Pb2L (3Ph)(mu-OH)]ClO4 (5) and [Pb2L (4Ph)(mu-OH)] ClO4 ( 6), respectively. Transmetallation of 5 with nickel(II) ions yields a novel, structurally characterized, dinickel(II) macrocyclic complex, [Ni2L (3Ph)(NCS)(2)] ( 7), which features double triazolate bridging of the two five-coordinate nickel(II) ions.
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