Copper(I) Coordination Polymers [{Cu(μ-X)}<sub>2</sub>{RP(μ-N<i><sup>t</sup></i><sup></sup>Bu)}<sub>2</sub>]<i><sub>n</sub></i> (R = OC<sub>6</sub>H<sub>4</sub>OMe-<i>o</i>; X = Cl, Br, and I) and Their Reversible Conversion into Mononuclear Complexes [CuX{(RP(μ-N<i><sup>t</sup></i><sup></sup>Bu))<
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The reactions of cyclodiphosphazane cis-[tBuNP(OC6H4OMe-o)]2 (1) with 2 equiv of CuX in acetonitrile afforded one-dimensional CuI coordination polymers [Cu2X2{tBuNP(OC6H4OMe-o)}2]n (2, X = Cl; 3, X = Br; 4, X = I). The crystal structures of 2 and 4 reveal a zigzag arrangement of [P(μ-N)2P] and [Cu(μ-X)2Cu] 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(I) complexes of the type [CuX{(tBuNP(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.
