Lobana Tarlok S, Castineiras Alfonso, Turner Peter
Department of Chemistry, Guru Nanak Dev University, Amritsar-143 005, India.
Inorg Chem. 2003 Jul 28;42(15):4731-7. doi: 10.1021/ic034010n.
The reactions of copper(I) halides with bis(diphenylselenophosphinyl)alkanes, namely Ph(2)P(Se)-(CH(2))(n)-P(Se)Ph(2) [n = 1-4], in acetonitrile are described. The ligand 1,3-bis(diphenylselenophosphinyl)propane [dppp-Se,Se] with copper(I) bromide and copper(I) iodide formed two unusual infinite coordination polymers, namely Cu(2)Br(2)(mu(2)-dppp-Se-Se)(2), 1, and Cu(3)I(3)(mu(2)-dppp-Se,Se)(2), 2. Selenium bridged dinuclear complexes, [Cu(2)Br(2)((mu(3)-dppm-Se,Se)(2)], 3, and [Cu(2)I(2)(dppm-Se,Se)(2)], 4, were formed using 1,1-bis(diphenylselenophosphinyl)methane [dppm-Se,Se]. Similarly, 1,2-bis(diphenylselenophosphinyl)ethane [dppe-Se,Se] and 1,4-bis(diphenylselenophosphinyl)butane [dppb-Se,Se] formed complexes, Cu(2)Br(2)(dppe-Se,Se)(2), 5, and Cu(2)I(2)(dppb-Se,Se), 6. These have been characterized with the help of analytical data, infrared spectroscopy, and, for compounds 1-3, X-ray crystallography. Compound 2, Cu(3)I(3(dppp-Se,Se)(2), has two dppp-Se,Se molecules coordinating to two copper(I) atoms of the dinuclear Cu(mu-I)(2)Cu core in unidentate fashion, with two pendant Ph(2)P(Se)- moieties in trans orientation, and one of these groups is coordinated to another copper(I) iodide moiety, thus forming the repeat unit (A), -CuI(mu-dppp-Se,Se)Cu(mu-I)(2)Cu(mu-dppp-Se,Se)-. This repeat unit (A) combined with another unit, and this process continued and finally formed the infinite polymer 2. In this polymer, the mononuclear CuISe(2) and dinuclear Cu(2)(mu-I)(2)Se(2) cores have distorted trigonal planar geometries around Cu centers. The Cu(2)...Cu(2)* separation of 2.643(1) A is less than twice the van der Waals radius of Cu, 2.80 A. The structure of polymer 1 is similar to that of 2, except that it has only mononuclear trigonal planar CuBrSe(2) units bridged by Se atoms of dppp-Se,Se ligand, and the repeat unit is -CuBr(mu(2)-dppp-Se,Se)CuBr(mu(2)(-)dppp-Se,Se)-. The formation of zigzag one-dimensional copper(I) coordination polymers (1 and 2), with trigonal planar copper(I) centers, provides the first examples of this type in tertiary phosphine chalcogenide chemistry. In contrast, the decrease in methylene chain length, from -(CH(2))(3)- to -(CH(2))-, resulted in chelation by the dppm-Se,Se ligand, forming CuBr(dppm-Se,Se), which dimerized via Se donor atoms and formed [Cu(2)Br(2)(mu(3)-dppm-Se,Se)(2)], 3. It has a relatively less common central kernel, Cu(mu-Se)(2)Cu, and each Cu atom is further bonded to one terminal Br and one Se atoms, and the geometry around each Cu center is distorted tetrahedral (bond angles, ca. 101-121 degrees).
本文描述了卤化亚铜（I）与双（二苯基硒代膦酰基）烷烃，即Ph₂P（Se）-（CH₂）ₙ-P（Se）Ph₂[n = 1 - 4]，在乙腈中的反应。配体1,3 - 双（二苯基硒代膦酰基）丙烷[dppp - Se,Se]与溴化亚铜（I）和碘化亚铜（I）形成了两种不寻常的无限配位聚合物，即[Cu₂Br₂（μ₂ - dppp - Se - Se）₂]ₙ，1，和[Cu₃I₃（μ₂ - dppp - Se,Se）₂]ₙ，2。使用1,1 - 双（二苯基硒代膦酰基）甲烷[dppm - Se,Se]形成了硒桥连双核配合物[Cu₂Br₂（（μ₃ - dppm - Se,Se）₂]，3，和[Cu₂I₂（dppm - Se,Se）₂]，4。类似地，1,2 - 双（二苯基硒代膦酰基）乙烷[dppe - Se,Se]和1,4 - 双（二苯基硒代膦酰基）丁烷[dppb - Se,Se]形成了配合物Cu₂Br₂（dppe - Se,Se）₂，5，和Cu₂I₂（dppb - Se,Se），6。这些配合物通过分析数据、红外光谱进行了表征，对于化合物1 - 3，还进行了X射线晶体学表征。化合物2，[Cu₃I₃（dppp - Se,Se）₂]ₙ，有两个dppp - Se,Se分子以单齿方式与双核Cu（μ - I）₂Cu核的两个亚铜（I）原子配位，有两个处于反式取向的悬垂Ph₂P（Se）-部分，其中一个这样的基团与另一个碘化亚铜（I）部分配位，从而形成重复单元（A），-CuI（μ - dppp - Se,Se）Cu（μ - I）₂Cu（μ - dppp - Se,Se）-。这个重复单元（A）与另一个单元结合，这个过程持续进行，最终形成了无限聚合物2。在这个聚合物中，单核CuISe₂和双核Cu₂（μ - I）₂Se₂核在Cu中心周围具有扭曲三角形平面几何构型。Cu₂...Cu₂*间距为2.643（1）Å，小于Cu的范德华半径的两倍，即2.80 Å。聚合物1的结构与2相似，不同之处在于它仅具有由dppp - Se,Se配体的Se原子桥连的单核三角形平面CuBrSe₂单元，并且重复单元是-CuBr（μ₂ - dppp - Se,Se）CuBr（μ₂（ - ）dppp - Se,Se）-。具有三角形平面亚铜（I）中心的锯齿状一维亚铜（I）配位聚合物（1和2）的形成，在叔膦硫属化物化学中提供了此类的首个实例。相比之下，亚甲基链长度从 - （CH₂）₃ - 减少到 - （CH₂） - ，导致dppm - Se,Se配体螯合，形成CuBr（dppm - Se,Se），其通过Se供体原子二聚并形成[Cu₂Br₂（μ₃ - dppm - Se,Se）₂]，3。它具有相对不太常见的中心核Cu（μ - Se）₂Cu，并且每个Cu原子进一步与一个末端Br和一个Se原子键合，每个Cu中心周围的几何构型是扭曲四面体（键角约为101 - 121度）。
