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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, computational studies of Mg complexes supported by 2,2′:6,2′′-terpyridine ligands
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Synthesis, computational studies of Mg complexes supported by 2,2′:6,2′′-terpyridine ligands

机译：2,2'：6,2''-吡啶吡啶配体支持的Mg配合物的合成，计算研究

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The reactions of the substituted 2,2′:6,2′′-terpyridine ligands, 4′-mesityl-2,2′:6′,2′′-terpyridine (mesitylterpy) (1a), 4,4′,4′′-tri-tert-butyl-2,2′: 6′,2′′-terpyridine (tri- ~tButerpy) (1b) and 4′-phenyl-2,2′:6′,2′′-terpyridine (phenylterpy) (1c) with Grignard reagents were investigated. When half an equivalent of mesitylterpy or tri- ~tButerpy were treated with MeMgBr in diethyl ether, the only products were (R-terpy)MgBr _2 (R = mesityl (5a), or tri- ~tBu (5b)) and Me _2Mg and a similar reaction was observed in THF. Compounds 5a and 5b were characterized by X-ray crystallography. Changing the Grignard reagent to PhMgBr also generated 5a and 5b along with Ph _2Mg, while the reaction between MeMgCl or PhMgCl and 1a or 1b generated (R-terpy)MgCl _2 (R = mesityl (6a), or tri- ~tBu (6b)) and either Me _2Mg or Ph _2Mg, respectively. The products from reactions between phenylterpy (1c) and Grignard reagents were highly insoluble and could not be fully characterized but appeared to be the same as those from reactions with 1a and 1b. In contrast to other studies using tridentate nitrogen ligands, which formed either mixed halide alkyl species or dihalide and bis(alkyl) species depending on whether the Grignard reagent was reacted with the ligand in diethyl ether or THF, the formation of mixed halide, alkyl complexes of the type (R-terpy)MgR′X (R′ = Me or Ph; X = Cl or Br) or dialkyl species such as (R-terpy)MgR′ _2 (R′ = Me or Ph) was not observed here, regardless of the reaction conditions. DFT studies were performed to complement the experimental studies. The experimental results could not be accurately reproduced unless π-stacking effects associated with free terpyridine were included in the model. When these effects were included, the calculations were consistent with the experimental results which indicated that the formation of the terpy Mg dihalide species and R′ _2Mg (R′ = Me or Ph) is thermodynamically preferred over the formation of mixed alkyl halide Mg species. This is proposed to be due to the increased steric bulk of the terpy ligand in the coordination plane, compared with other tridentate nitrogen donors.
机译：取代的2,2'：6,2''-吡啶吡啶配体，4'-mesityl-2,2'：6'，2''-terridine（mesitylterpy）（1a），4,4'，4的反应′′-三叔丁基-2,2′：6′，2′′-吡啶（tri-〜tButerpy）（1b）和4′-苯基-2,2′：6′，2′′-吡啶（Germanard试剂）（苯基对）（1c）进行了研究。当在乙醚中用MeMgBr处理一半当量的均三甲苯或三叔丁醚时，唯一的产物是（R-叔丁基）MgBr _2（R =均三甲苯（5a）或三叔丁基（5b））和Me _2Mg在THF中观察到类似的反应。化合物5a和5b通过X射线晶体学表征。将Grignard试剂更改为PhMgBr还会与Ph _2Mg一起生成5a和5b，而MeMgCl或PhMgCl与1a或1b之间的反应生成（R-terpy）MgCl _2（R =均三（6a），或tri-〜tBu（6b ））和Me _2Mg或Ph _2Mg。苯基萜基（1c）与格利雅试剂之间反应产生的产物高度不溶，无法完全表征，但似乎与1a和1b反应产生的产物相同。与其他使用三齿氮配体的研究相反，三齿氮配体形成混合的卤化物烷基物种或二卤化物和双（烷基）物种，具体取决于格利雅试剂是否与配体在乙醚或THF中反应，形成了混合卤化物，烷基络合物（R-terpy）MgR'X（R'= Me或Ph; X = Cl或Br）类型或二烷基物质如（R-terpy）MgR'_2（R'= Me或Ph） ，无论反应条件如何。进行了DFT研究以补充实验研究。除非模型中包含与游离叔吡啶有关的π堆积效应，否则无法准确地再现实验结果。当包括这些影响时，计算结果与实验结果相符，实验结果表明，在热力学上，形成叔丁基Mg二卤化物和R'_2Mg（R'= Me或Ph）比形成混合烷基卤化物Mg更好。提出这是由于与其他三齿氮供体相比，叔丁基配体在配位平面中的空间体积增加。

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