Mononuclear, Tetranuclear and 1D Polymeric Copper(I) Complexes of Large Bite Bisphosphines Containing Nitrogen and Oxygen Donor Atoms

Abstract

AbstractThe syntheses of new bisphosphines containing nitrogen and oxygen donor atoms, N,N‐bis(diphenylphosphinobenzyl)‐N‐phenylamine (PNP) (1), bis(2‐diphenylphosphinobenzyl) ether (POP) (2) and their coordination chemistry with copper(I) halides have been explored. The ligand structure plays a major role in controlling the coordination sphere and the structural features of copper(I) complexes. The reaction of 1 with CuX (X = Cl, Br, I) in 1:2 molar ratio yielded tetranuclear cuboid complexes [Cu4(μ‐X)4{C6H5N(CH2‐2‐C6H4PPh2)2}2‐P,P] (3–5), whereas the similar reactions of 2 afforded tetranuclear stair‐step type complexes [Cu4(μ2‐X)2(μ3‐X)2{O(CH2‐2‐C6H4PPh2)2}2‐P,P] (9–11). The reactions of 1 with CuX in 1:1 molar ratio afforded 1D coordination polymers [CuX{C6H5N(CH2‐2‐C6H4PPh2)2}‐P,P]n, (6–8). The reaction of CuI with 2 in a 1:1 molar ratio also yielded a tetranuclear stair‐step complex [Cu4(μ2‐I)2(μ3‐I)2{O(CH2‐2‐C6H4PPh2)2}2‐P,O,P] (12) but with tridentate P,O,P coordination along with 11, whereas the similar reaction with CuCl gave a simple mononuclear complex [CuCl{O(CH2‐2‐C6H4PPh2)2}‐P,O,P] (13). In both the complexes, the ligand 2 exhibits a tridentate mode of coordination. Many of these complexes have been structurally characterized.