Coordination complexes of the bismuth(III) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridine ligands
Coordination complexes of the bismuth(III) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridine ligands
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硫醇铋(III) Bi(SC6F5)3 和 Bi(SC6Cl5)3 与吡啶配体的配位络合物
DOI：
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发表时间：
2003
期刊：
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通讯作者：
J. Starbuck
中科院分区：
文献类型：
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作者：
K. M. Anderson;Christian J. Baylies;A. H. M. M. Jahan;N. C. Norman;A. Orpen;J. Starbuck
氯芳基硫醇铋Bi（SC 6Cl 5）3通过与前述氟芳基物质Bi（SC 6 F5）3的合成类似的方法由BiPh 3和硫醇HSC 6Cl 5之间的反应制备。化合物Bi（SC 6Cl 5）3仅微溶，但可以作为dmf加合物[Bi（SC 6Cl 5）3（dmf）2]分离。
(dmf =
N，N-二甲基甲酰胺），其采用基于五坐标正方形的金字塔几何结构，其中两个dmf配体位于底面，具有相互顺式构型。Bi（SC 6 F5）3或Bi（SC 6Cl 5）3分别与吡啶或2，2 ′-联吡啶配体反应得到配合物fac-[Bi（SC 6 F5）3（py）3]。
(two结晶多晶型物），fac-[Bi（SC 6Cl 5）3（py）3]，fac-[Bi（SC 6 F5）3（4-pic）3]
（4-pic = 4-甲基吡啶），[Bi（SC 6Cl 5）3（4-pic）2]，[Bi（SC 6 F5）3（bipy）]
(bipy= 2，2 ′-联吡啶）、[Bi（SC 6Cl 5）3（bipy）]、[Bi 2（SC 6Cl 5）6（2-pic）3]
（2-pic = 2-甲基吡啶）和[Bi（SC 6 F5）3（4-pic）]。五配位和四配位配合物分别采用正方形的金字塔和赤道空的三角双金字塔（双楔）几何结构，前者具有两个配体在基面上彼此顺式。化合物[Bi 2（SC 6Cl 5）6（2-pic）3]含有五配位和四配位单核单元。还分离出具有式[4-picH][（4-pic）2 H][Bi 3（SC 6 F5）11]的盐，其中阴离子含有键合到具有基于正方形的金字塔几何形状的五个硫醇盐配体的中心铋。两个顺式基础硫醇盐作为桥接基团的两个外部铋中心，其中每个中心是四坐标与预期的双楔型几何形状，其中桥接硫醇盐是在轴向位置。本文还报道了双核芳基硫醇铋化合物[Bi_2 Ph_2（SC_6 F_5）_4（4-pic）_2]的结构。所有结构中的分子内构象和分子间缔合都由π-π-相互作用控制。
The chloro-aryl bismuth thiolate Bi(SC6Cl5)3 has been prepared from the reaction between BiPh3 and the thiol HSC6Cl5 by analogy with the previously described synthesis of the fluoro-aryl species Bi(SC6F5)3. The compound Bi(SC6Cl5)3 is only sparingly soluble but can be isolated as a dmf adduct [Bi(SC6Cl5)3(dmf)2]
(dmf =
N,N-dimethylformamide) which adopts a five-coordinate square-based pyramidal geometry in which the two dmf ligands lie in the basal plane with a mutually cis configuration. Treatment of either Bi(SC6F5)3 or Bi(SC6Cl5)3 with pyridine or 2,2′-bipyridyl ligands affords the coordination complexes fac-[Bi(SC6F5)3(py)3]
(two crystalline polymorphs), fac-[Bi(SC6Cl5)3(py)3], fac-[Bi(SC6F5)3(4-pic)3]
(4-pic = 4-picoline), [Bi(SC6Cl5)3(4-pic)2], [Bi(SC6F5)3(bipy)]
(bipy = 2,2′-bipyridyl), [Bi(SC6Cl5)3(bipy)], [Bi2(SC6Cl5)6(2-pic)3]
(2-pic = 2-picoline) and [Bi(SC6F5)3(4-pic)]. Five- and four-coordinate complexes adopt square-based pyramidal and equatorially vacant, trigonal bipyramidal (disphenoidal) geometries respectively, the former having the two ligands cis to each other in the basal plane. The compound [Bi2(SC6Cl5)6(2-pic)3] contains both five- and four-coordinate mononuclear units. A salt with the formula [4-picH][(4-pic)2H][Bi3(SC6F5)11] was also isolated in which the anion contains a central bismuth bonded to five thiolate ligands with a square-based pyramidal geometry. Two cis-basal thiolates act as bridging groups to two outer bismuth centres each of which is four-coordinate with the expected disphenoidal geometry in which the bridging thiolate is in an axial position. The structure of the dinuclear arylbismuth thiolate compound [Bi2Ph2(SC6F5)4(4-pic)2] is also described. Intramolecular conformations and intermolecular associations in all structures are dominated by π–π-interactions.