First Example of Cage P(4)N(4)-Macrocycle Copper Complexes with Intracavity Location of Unusual Cu(2)I Fragments

In this study, 28-membered macrocyclic 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane were synthesized by condensation of pyridinephosphine, paraformaldehyde, and primary diamines (bis(4-aminophenyl)methane or -sulfide. The first representatives of binuclear copper(I) complexes of P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into a macrocyclic core and intracavity location of unusual, developed angle Cu(2)I moiety were obtained. The structure of one complex was established by X-ray diffraction analysis. The complexation led to a slight distortion of the cyclophane conformations.