Binuclear Copper(II), Nickel(II), Cobalt(II) and Zinc(II) Complexes of the Macrocycle, 1,4,7,16,19,22-hexaaza [9.9] metacyclophane (L). Crystal Structure of [Cu₂LCl₄]_0.5.[Cu₂LCl₃ClO₄.dmf and the Copper(II) Complex Catalysed Hydrolysis of the Phosphotriester 2,4-Dinitrophenyl-diethylorthophosphate

Copper(II), nickel(II), cobalt(II) and zinc(II) complexes of the 22-membered hexa-aza macrocycle 1,4,7,16,19,22-hexa-aza[9.9]metacyclophane (L) have been prepared and characterised. The crystal structure of a copper(II) chloro complex has been determined. The complex exists in two forms, one form (Type 1) with an inversion centre has both copper atoms in essentially square pyramidal stereochemistry with an N3Cl2 donor set and a Cu ... Cu distance of 5.82 Angstrom. The other form (Type II) has one square pyramidal copper with an N3Cl2 donor set and one planar copper with an N3Cl donor set. The Type II Cu ... Cu distance is 6.13 Angstrom. The structure is best described as [Cu2LCl4](0.5).[Cu2LCl3]ClO4. dmf (dmf = N,N-dimethylformamide). The copper(II) complex catalyses the hydrolysis of the phosphotriester 2,4-dinitrophenyldiethylphosphate to give diethyl phosphate and the mechanism of the reaction is discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.