Caged phosphite complexes of copper(I) halides

摘要

The coordination chemistry of the caged phosphites 4-methyl-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (MeCage) and 4-nitro-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octane (NO(2)Cage) 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(NO(2)Cage)](4), [CuX(MeCage)(2)](2), [CuX(NO(2)Cage)(2)](2), and [CuX(MeCage)(3)]. Recrystallization of [CuBr(NO(2)Cage)(2)](2) in MeCN produced [CuBr(NO(2)Cage)(NCMe)](2). Three X-ray crystal structures are reported: [CuCl(MeCage)](4) (I - 4, a = 13: 4292(5) Angstrom, b = 13.4292(5) Angstrom, c = 9.4641(5) Angstrom, V = 1706.79(13) Angstrom(3), Z = 2), [CuBr(MeCage)(2)](2) (I4(1)/a, a = 19.5751(17) Angstrom, b = 19.5751(17) Angstrom, c = 16.4513(15) Angstrom, V = 6303.9(10) Angstrom(3), Z D 8), and [CuBr(NO(2)Cage)(NCMe)](2) (P2(1)/c, a = 9.0506(4) Angstrom, b = 15.2428(7) Angstrom, c = 8.8673(4) Angstrom, beta = 109.7640(10)degrees, V = 1151.24(9) Angstrom(3), Z = 2). [References: 15]