Copper(II) complexes of the 14-membered cis-N2S2 macrocycle 14,14,16-trimethyl-2,6-dithia-13,17-diazatricyclo[16.4.0.07,12]docosa-1(18),7(12),8,10,16,19,21-heptaene

Abstract

The ligand 14,14,16-trimethyl-2,6-dithia-13,17-diazatricyclo[16.4.0.0^7,12]docosa-1(18),7(12),8,10,16,19,21-heptaene (L) has been prepared by hydrolysis of the nickel(II) complex [NiLBr₂]. A variety of copper(II) complexes CuL(ClO₄)₂, CuLBr₂, CuLCl₂, CuL(NO₃)₂·H₂O, and CuL(O₂CMe)₂ have been characterised and their spectroscopic properties studied. The complexes do not display a reversible Cu^II–Cu^I couple in acetonitrile solution, presumably as a result of the rigid nature of the macrocycle which does not readily adapt to the preferred tetrahedral stereochemistry of copper(I).