Caged phosphite complexes of copper(I) halides

The coordination chemistry of the caged phosphites 4-2,6,7-trioxa-1-phosphabicyclo [2.2.2]octane (MeCage) and 4-nitro-t2,6,7-trioxa-1t-phosphabicyclo[2.2.2]octane (NO2Caget) with copper(I) halides is reported. Reactions of CuX = CuCl, CuBr, and CuI with the phosphite ligands afford complexes of the type [CuX(MeCage)]4, [CuX(NO2Cage)]4, [CuX(MeCage)2]2, [CuX(NO2Cage)2]2, and [CuX(MeCage)3]. Recrystallization of [CuBr(NO2Cage)2]2 in MeCN produced [CuBr(NO2Cage)(NCMe)]2. Three X-ray crystal structures are reported: [CuCl(MeCage)]4 (I − 4, a = 13.4292(5) A, b = 13.4292(5) A, c = 9.4641(5) A, V = 1706.79(13) A3, Z = 2), [CuBr(MeCage)2]2 (I41/a, a = 19.5751(17) A, b = 19.5751(17) A, c = 16.4513(15) A, V = 6303.9(10) A3, Z = 8), and [CuBr(NO2Cage)(NCMe)]2 (P21/c, a = 9.0506(4) A, b = 15.2428(7) A, c = 8.8673(4) A, β = 109.7640(10)○, V = 1151.24(9) A3, Z = 2).