Halide and substituent dependent structural variation in copper(i) halide complexes of 1,5,9-triphosphacyclododecanes

Abstract

The reactions of 1,5,9-triethyl-1,5,9-triphosphacyclododecane, [12]-ane-P₃Et₃, and 1,5,9-tri(2-propyl)-1,5,9-triphosphacyclododecane, [12]-ane-P₃ⁱPr₃ with copper(I)halides produce either bimetallic species of the type [([12]-ane-P₃R₃)Cu(CuX₂)] (X = halide) or monomeric [([12]-ane-P₃R₃)CuX] depending on the nature of the halide and, to a lesser extent, the macrocycle. With CuCl only bimetallic complexes are formed with one copper centre bound to the macrocycle and a second attached through a Cu–Cu bond with a mono bridging chloride. CuBr affords monomeric [([12]-ane-P₃R₃)CuBr] complexes when performed in a 1 : 1 M : L ratio whereas the bimetallic compound [([12]-ane-P₃Et₃)(CuBr)₂], resulted when a 2 : 1 ratio of M : L was employed. With CuI in all ratios only monomeric complexes were obtained. The synthesised complexes have been fully characterised by spectroscopic and analytical techniques and by determination of the molecular structures by single-crystal X-ray diffractometry.