Do solid-state structures reflect Lewis acidity trends of heavier group 13 trihalides? Experimental and theoretical case study.
Do solid-state structures reflect Lewis acidity trends of heavier group 13 trihalides? Experimental and theoretical case study.
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固态结构是否反映了较重的 13 族三卤化物的路易斯酸度趋势？
DOI：
10.1021/ic301507c
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发表时间：
2012
影响因子：
4.6
通讯作者：
A. V. Butlak
中科院分区：
文献类型：
--
作者：
A. Timoshkin;M. Bodensteiner;T. N. Sevastianova;A. Lisovenko;E. I. Davydova;M. Scheer;C. Grassl;A. V. Butlak
基于X射线和密度泛函理论的联合研究，考虑了铝和镓的卤化物的刘易斯酸性趋势。用X-射线衍射法首次确定了重13族元素三卤化物MX（3）（M = Al，Ga; X = Cl，Br，I）与单齿含氮给体Py，pip，NEt（3）的配合物结构以及AlCl（3）·PPh（3）加合物的结构。对MX（3）与含氮、磷、砷和氧的给体配体之间的结构表征络合物的广泛理论研究（B3 LYP/TZVP理论水平）使我们能够建立刘易斯酸趋势Al > Ga，Cl> Br > I。通过对实验和理论结果的分析，指出固态掩盖了卤化铝的刘易斯酸性趋势。气相中AlCl（3）·D和AlBr（3）·D配合物之间的Al-N键距差异很小，而在凝聚相中，观察到9-芴酮、mdta和NEt（3）给体的AlBr（3）·D配合物的Al-N键距较短。提出了基于固体加合物分子间（H···X）相互作用的模型来解释这一现象。因此，固体配合物中的给体-受体键距不能总是用作刘易斯酸性的标准。
Lewis acidity trends of aluminum and gallium halides have been considered on the basis of joint X-ray and density functional theory studies. Structures of complexes of heavier group 13 element trihalides MX(3) (M = Al, Ga; X = Cl, Br, I) with monodentate nitrogen-containing donors Py, pip, and NEt(3) as well as the structure of the AlCl(3)·PPh(3) adduct have been established for the first time by X-ray diffraction studies. Extensive theoretical studies (B3LYP/TZVP level of theory) of structurally characterized complexes between MX(3) and nitrogen-, phosphorus-, arsenic-, and oxygen-containing donor ligands have allowed us to establish the Lewis acidity trends Al > Ga, Cl ≈ Br > I. Analysis of the experimental and theoretical results points out that the solid state masks the Lewis acidity trend of aluminum halides. The difference in the Al-N bond distances between AlCl(3)·D and AlBr(3)·D complexes in the gas phase is small, while in the condensed phase, shorter Al-N distances for AlBr(3)·D complexes are observed with 9-fluorenone, mdta, and NEt(3) donors. The model based on intermolecular (H···X) interactions in solid adducts is proposed to explain this phenomenon. Thus, the donor-acceptor bond distance in the solid complexes cannot always be used as a criterion of Lewis acidity.
影响因子：
2.8
作者：
Hilt, Gerhard;Puenner, Florian;Bohn, Martin A.
通讯作者：
Bohn, Martin A.