Structural studies on phenyl bismuth halides and halogenoanions
Structural studies on phenyl bismuth halides and halogenoanions
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苯基卤化铋和卤代阴离子的结构研究
DOI：
10.1039/dt9920001967
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发表时间：
1992
期刊：
影响因子：
--
通讯作者：
S. Stratford
中科院分区：
文献类型：
--
作者：
W. Clegg;R. Errington;G. A. Fisher;David C. R. Hockless;N. C. Norman;A. Orpen;S. Stratford
用X射线晶体学对一系列苯基铋卤化物和卤阴离子进行了结构研究。配合物[BiPhBr 2（thf）]1和[BiPhI 2（thf）]2（thf =四氢呋喃）在每对相邻的铋原子之间形成了一个单一的不对称桥接卤化物的一维聚合物链。铋中心周围的配位几何形状是一个正方形的金字塔与苯基在顶端的位置和两个顺式卤化物，桥卤化物从相邻的单体单元和一个THF配体在基面。[NEt 4]I与2加成得到离子型[NEt 4]2[Bi 2 Ph 2 I6]·Et 2 O3，其中含有离散的二聚体[Bi 2 Ph 2 I6]2-阴离子。这种阴离子包括两个共享边缘的正方形金字塔，底面之间的角度为105.2°。与1和2一样，苯基占据顶端位点，每个铋周围的基底位点被两个末端和两个桥接碘化物占据。配合物[BiPh_2Br（thf）]_5是单体，在铋中心附近具有赤道空位三角双锥配位几何构型，其中苯基占据赤道位置，溴和thf配体占据轴向位置。[PPh 4][BiPh 2Br 2]6的结构含有单体[BiPh 2Br 2]-阴离子，其几何形状与5中发现的相似。比较，在适当的情况下，与相关的碲（IV）化合物，并讨论了在配合物中的键合的性质，特别是关于的细节，在结构中观察到的二级分子间键1-3。
Structural studies by X-ray crystallography have been carried out for a range of phenyl bismuth halides and halogenoanions. The complexes [BiPhBr2(thf)]1 and [BiPhI2(thf)]2(thf = tetrahydrofuran) form one-dimensional polymeric chains with a single asymmetrically-bridging halide between each pair of adjacent bismuth atoms. The co-ordination geometry around the bismuth centre is that of a square-based pyramid with the phenyl group in the apical position and two cis halides, a bridging halide from an adjacent monomer unit and a thf ligand in the basal plane. Addition of [NEt4]I to 2 affords the ionic species [NEt4]2[Bi2Ph2I6]·Et2O 3 which contains the discrete dimeric [Bi2Ph2I6]2– anion. This anion comprises two edge-shared square-based pyramids with an angle of 105.2° between the basal planes. As with 1 and 2, the phenyl group occupies the apical site with the basal sites around each bismuth occupied by two terminal and two bridging iodides. The complex [BiPh2Br(thf)]5 is monomeric and has an equatorially vacant trigonal-bipyramidal co-ordination geometry around the bismuth centre in which the phenyl groups occupy the equatorial sites and the bromine and thf ligand the axial sites. The structure of [PPh4][BiPh2Br2]6 contains monomeric [BiPh2Br2]– anions with a geometry similar to that found in 5. Comparisons are made, where appropriate, with related tellurium(IV) compounds, and the nature of the bonding in the complexes is discussed particularly with regard to the details of the secondary, intermolecular bonds observed in the structures of 1–3.