Copper(I) coordination polymers[{Cu(mu-X)}(2){RP(mu-(NBu)-Bu-t)}(2)](n) (R = OC6H4OMe-o; X = Cl, Br, and I) and their reversible conversion into mononuclear complexes [CuX{(RP(mu-(NBu)-Bu-t))(2)}(2)]: Synthesis and structural characterization

Abstract

The reactions of cyclodiphosphazane cis-[(BuNP)-Bu-t(OC6H4OMe-o)](2) (1) with 2 equiv of CuX in acetonitrile afforded one-dimensional Cu-I coordination polymers [Cu2X2 {(BuNP)-Bu-t(OC6H4OMe-o)}(2)](n) (2, X) Cl; 3, X) Br; 4, X = 1). The crystal structures of 2 and 4 reveal a zigzag arrangement of [P(mu - N)(2)P] and [Cu(mu - X)(2)Cu] units in an alternating manner to form one- dimensional CuI coordination polymers. The reaction between 1 and CuX in a 2: 1 ratio afforded mononuclear tricoordinated copper(II) complexes of the type [CuX {((BuNP)-Bu-t(OC6H4OMe-o))(2)}(2)] (5, X) Cl; 6, X) Br; 7, X = I). The single-crystal structures were established for the mononuclear copper(I) complexes 5 and 6. When the reactant ratios are 1: 1, the formation of a mixture of polymeric and mononuclear products was observed. The CuI polymers (2 - 4) were converted into the mononuclear complexes ( 5 - 7) by reacting with 3 equiv of 1 in dimethyl sulfoxide. Similarly, the mononuclear complexes (5 - 7) were converted into the corresponding polymeric complexes (2 - 4) by reacting with 3 equiv of copper(I) halide under mild reaction conditions.