Transition-metal complexes of the macrocyclic ligand 5,12-dimethyl-1,4,8,11-tetra-azacyclotetradeca-4,11-diene

Abstract
The macrocyclic ligand 5,12-dimethyl-1,4,8,11-tetra-azacyclotetradeca-4,11-diene (L1) has been prepared as its dihydroperchlorate salt by the reaction of ethane-1,2-diamine monohydroperchlorate with methyl vinyl ketone. A transoid arrangement of the imine linkages has been confirmed by a crystallographic study on trans-[CoL1(SCN)2]-SCN·H2O. A number of metal(II) complexes [ML1][ClO4]2(M = Ni, Cu, Co, or Zn) have been prepared. In addition a series of octahedral cobalt(III) complexes of the general type trans-[CoL1X]n+(X = Cl, Br, NO2 , SCN, or NH3) and cis-[CoL1(aa)]n+(aa = CO3 2– or acac) have been synthesised. Two separate isomers of trans-[CoL1Cl2][ClO4]2 have been identified corresponding to the rac- and meso-diastereoisomers resulting from the asymmetric secondary nitrogen donors. The co-ordination chemistry of L1 is discussed and i.r. and dd electronic spectra are reported.

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