Bismuth-Arene π-Interaction: A Combined Experimental and Theoretical Approach
Bismuth-Arene π-Interaction: A Combined Experimental and Theoretical Approach
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DOI：
10.1021/om900536r
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发表时间：
2009-09-28
期刊：
影响因子：
2.8
通讯作者：
Mehring, Michael
中科院分区：
文献类型：
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作者：
Auer, Alexander A.;Mansfeld, Dirk;Mehring, Michael
用X-射线单晶结构分析对三有机铋化合物[Bi(CH2C6H4Cl2)(3)](2)(2)(2)进行了表征，结果表明，铋-北极区的pi配位作用和pi-pi堆积作用形成了一个二维网络，其间距分别为3.659埃(铋芳烃质心)和3.869埃(北极质心)。为了阐明这种成键情况的性质，进行了量子力学研究。此外，为了更好地理解铋-芳烃的配位，在BSSE修正的MP2/TZVP理论水平上，对几种BiX3中心点C6H6(X=H，Me，OH，OMe，F，Cl，Br.)模型化合物进行了详细的理论研究。模型化合物BiMe_3中心点C_6H_6(类似于3.75埃)和铋(OMe)(3)中心点C_6H_6(类似于3.35埃)中铋-芳烃距离的计算值分别为3.659埃和3.340埃，与[Bi(CH_2C_6H_4Cl-2)(3)](2)(2)和[Bi(OSiPh(2)Tbu)(3)](2)(1)的实验值相吻合。模型化合物的相互作用能范围从BiMe3中心点C6H6的7kJ/mol到BiBr3中心点C6H6的41kJ/mol。
The triorgano bismuth compound [Bi(CH2C6H4Cl-2)(3)](2) (2) was characterized by an X-ray single-crystal structure analysis, which reveals the formation of a two-dimensional network as a result of bismuth-arctic pi-coordination and pi-pi-stacking interactions with distances of 3.659 angstrom (bismuth-arene(centroid)) and 3.869 angstrom (arctic centroids), respectively. In order to elucidate the nature of this bonding situation, a quantum mechanical study was carried out. Additionally, a detailed theoretical study on several model compounds of the type BiX3 center dot C6H6 (X = H, Me, OH, OMe, F, Cl, Br) was carried out at the BSSE-corrected MP2/TZVP level of theory in order to develop a better understanding of the bismuth-arene coordination. The calculated bismuth-arene distances in the model compounds BiMe3 center dot C6H6 (similar to 3.75 angstrom) and Bi(OMe)(3)center dot C6H6 (similar to 3.35 angstrom) compare well with experimental values for [Bi(CH2C6H4Cl-2)(3)](2) (2) and [Bi(OSiPh(2)tBU)(3)](2) (1) of 3.659 and 3.340 angstrom, respectively. Interaction energies for the model compounds range from 7 kJ/mol for BiMe3 center dot C6H6 to 41 kJ/mol for BiBr3 center dot C6H6.