Mono- and binuclear tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate bismuth(III) dichloride complexes: a soft scorpionate ligand can coordinate to p-block elements.
Mono- and binuclear tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate bismuth(III) dichloride complexes: a soft scorpionate ligand can coordinate to p-block elements.
复制标题
单核和双核三(3-叔丁基-2-亚硫基-1H-咪唑-1-基)硼氢化铋(III)二氯化物配合物：软蝎形配体可以与p区元素配位。
DOI：
10.1107/s2053229616010615
复制
发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Szilagyi,RobertK
中科院分区：
文献类型：
--
作者：
Fujisawa,Kiyoshi;Kuboniwa,Ayaka;Kiss,Mercedesz;Szilagyi,RobertK
三（吡唑基）硼氢化物配体由于易于在吡唑环上引入空间和电子取代而被用于无机和配位化学领域。三（吡唑基）硼氢化物配体（称为“蝎子配体”）的开发和使用是由已故的Swiatoslaw Trofimenko教授开创的。他通过引入3-叔丁基和3-苯基取代基为他的配体系统开发了第二代，这种新的配体系统在稳定单体物种同时保持开放配位位点方面在无机和配位化学中取得了许多显着的发展。铋在有毒的重金属p区元素中是非常无害的，现在正成为铅等剧毒金属元素的替代品。合成了两种含硫阴离子三脚架型三（3-叔丁基-2-亚硫基-1H-咪唑-1-基）硼氢化物的铋（III）配合物。通过在甲醇/二氯甲烷中重结晶，得到二氯（甲醇-κO）[三（3-叔丁基-2-亚硫基-1H-咪唑-1-基-κS）硼氢化]铋（III）[Bi（C21 H34 BN 6S 3）Cl 2（CH 4 O）]，（I）的橙子晶体，显示单核结构。在非配位溶剂中，得到了具有氯桥连的双核结构的红色晶体，即二-μ-氯代-双{氯代[三（3-叔丁基-2-亚硫基-1H-咪唑-1-基-κS）硼氢化]铋（III）}，[Bi_2（C_（21）H_（34）BN_6S_3）_2Cl_4]，（II）。这些配合物具有{BiIIIS 3Cl 2 O}和{BiIIIS 3Cl 3}的配位几何构型，在（I）和（II）中的平均BiIII-S键长分别为2.73和2.78 π。 由于立体化学活性孤对，整体BiIII配位几何形状是扭曲的八面体。（I）中的三个BiIII-S键长几乎相等，但在（II）中表现出相当大的差异，其中一个较长，两个较短的距离也与UV-Vis和1H NMR光谱的变化相关。对于直接测量的Bi-S/Cl配位，配体K-边X-射线吸收测量进行了结合地面和激发态电子结构分析。对于p-区元素，这些含硫配体由于其灵活的配位几何形状而可用于制备适当的配合物。
Tris(pyrazolyl)hydroborate ligands have been utilized in the fields of inorganic and coordination chemistry due to the ease of introduction of steric and electronic substitutions at the pyrazole rings. The development and use of the tris(pyrazolyl)hydroborate ligand, called a `scorpionate', were pioneered by the late Professor Swiatoslaw Trofimenko. He developed a second generation for his ligand system by the introduction of 3-tert-butyl and 3-phenyl substituents and this new ligand system accounted for many remarkable developments in inorganic and coordination chemistry in stabilizing monomeric species while maintaining an open coordination site. Bismuth is remarkably harmless among the toxic heavy metal p-block elements and is now becoming popular as a replacement for highly toxic metal elements, such as lead. Two bismuth(III) complexes of the anionic sulfur-containing tripod tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate ligand were prepared. By recrystallization from MeOH/CH2Cl2, orange crystals of dichlorido(methanol-κO)[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III), [Bi(C21H34BN6S3)Cl2(CH4O)], (I), were obtained, manifesting a mononuclear structure. By using a noncoordinating solvent, red crystals of the binuclear structure with bridging Cl atoms were obtained, namely di-μ-chlorido-bis{chlorido[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III)}, [Bi2(C21H34BN6S3)2Cl4], (II). These complexes show {BiIIIS3Cl2O} and {BiIIIS3Cl3} coordination geometries with average BiIII—S bond lengths of 2.73 and 2.78 Å in (I) and (II), respectively. The overall BiIII coordination geometry is distorted octahedral due to stereochemically active lone pairs. The three BiIII—S bond lengths are almost equal in (I) but show considerable differences in (II), with one long and two shorter distances that also correlate with changes in the UV–Vis and 1H NMR spectra. For direct measurements of the Bi—S/Cl coordination, ligand K-edge X-ray absorption measurements were carried out in combination with ground and excited-state electronic structure analyses. For p-block elements, these sulfur-containing ligands are useful for preparing the appropriate complexes due to their flexible coordination geometry.