Copper and related metal complexes with NN′-(1,7,7-trimethylbicyclo-[2.2.1]heptane-2,3-diylidene)dianiline ligands

Abstract

Reactions of the title ligands [L¹(R = H), L²(R =p-Me), or L³(R =o-Me in the aniline ring)] with the appropriate bivalent metal salts yield the following complexes: [MCl₂L](M = Cu, L = L¹, L², or L³; M = Zn or Pd, L = L² or L³), [CuBr₂L²], and [M(BF₄)₂L₂](M = Cu, L = L¹, L², or L³; M = Ni or Zn, L = L¹ or L³). The complexes have been characterised by a variety of physicochemical techniques, and structures are proposed; [CuCl₂L], pseudo-tetrahedral and [Cu(BF₄)₂L₂], distorted tetragonal. Co-ordination of the [BF₄]^– ion is strongest for the L³ ligand complexes. Analogous copper(I) complexes have been synthesised and formulated as [CuL₂][CuCl₂](L = L¹, L², or L³), as well as a related complex [CuL⁴₂] of a thiaether ligand L⁴.