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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >On the consequences of the stereochemical activity of the Bi(iii) 6s(2) lone pair in cyclen-based complexes. The [Bi(DO3A)] case
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On the consequences of the stereochemical activity of the Bi(iii) 6s(2) lone pair in cyclen-based complexes. The [Bi(DO3A)] case

机译：基于循环基配合物中Bi（III）6S（2）静脉对的立体化学活性的后果。 [BI（DO3A）]案例

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We report a detailed study of the structure of the [Bi(DO3A)] complex both in the solid state and in solution. The X-ray crystal structure of [Bi(DO3A)] evidences the octa-coordination of the Bi(iii) ion, which is directly coordinated to the four nitrogen atoms of the cyclen unit and three oxygen atoms of the carboxylate groups. The octa-coordination is completed by an oxygen atom of a neighboring carboxylate group, which bridges Bi(iii) ions thanks to (2)-(1):(1) coordination, resulting in the formation of a coordination polymer. The Bi(iii) ion presents a twisted-square antiprismatic (TSAP) coordination geometry associated with the ()/() enantiomeric pair. A computational DFT study indicates that the 6s(2) lone pair of Bi(iii) is stereochemically active in [Bi(DO3A)] and most of the cyclen-based complexes reported in the literature. Depending on the spatial arrangement of the donor atoms of the ligand the lone pair points in different directions, so that Bi(iii) can easily accommodate different coordination environments. In solution the [Bi(DO3A)] complex exists as a monomeric complex, as demonstrated by DOSY measurements. The stability constant of the [Bi(DO3A)] complex, determined by using batch spectrophotometric titrations, was found to be rather high (logK = 26.85(5)). The complex presents characteristic absorption in the UV spectrum at 299 nm (epsilon = 8770 M-1 cm(-1)) that was attributed to the Bi(iii)-centered 6p 6s band on the basis of TDDFT calculations. Spectrophotometric titrations reveal weak binding of different anions to the [Bi(DO3A)] complex, with association constants of K-11 = 3.55(8), 3.09(7), 6.2(1) and 2.19(5) for Cl-, Br-, I- and N-3(-), respectively.
机译：我们都在固态和溶液报告[碧（DO3A）复杂结构的详细研究。的X射线晶体结构[铋（DO3A）]能证明铋（III）离子，其直接配位到环烯单元的四个氮原子和羧酸酯基团的三个氧原子的八协调。 （1）:( 1）协调，从而导致配位聚合物的形成 - 将辛协调由相邻羧酸酯基团的氧原子，其桥接铋（III）离子由于（2）完成。铋（III）离子的礼物扭绞方反棱柱（TSAP）协调与（）/（）的对映体对相关联的几何形状。甲计算DFT研究表明，6S（2）的孤对电子的Bi（III）是立体化学活性在[铋（DO3A）]和大多数环烯基配合物的文献报道。取决于本的供体原子的空间排列不同的方向和配体的孤对分，以便铋（III）可以很容易地适应不同的配位环境。在溶液中的[双（DO3A）]络合物形式存在的单体配合物，通过DOSY测量所证实。的稳定性常数[铋（DO3A）]络合物，通过使用批量分光光度滴定来确定，被发现是相当高的（的logK = 26.85（5））。在299纳米的紫外光谱的复杂呈现特征吸收（ε-= 8770 M-1厘米（-1）），这是归因于铋（III）计算TDDFT的基础上-centered 6P 6S频带。光度法滴定显示弱到[铋（DO3A）]络合物不同阴离子的结合，具有的缔合常数K-11 = 3.55（8），3.09（7），6.2（1）和2.19（5），用于氯离子，溴 - ，I-和N-3（ - ），分别。

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