Synthesis and Reactivity of Magnesium Complexes Supported by Tris(2-dimethylaminoethyl)amine (Me6tren)
Synthesis and Reactivity of Magnesium Complexes Supported by Tris(2-dimethylaminoethyl)amine (Me6tren)
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DOI：
10.1021/om4002186
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发表时间：
2013-05-13
期刊：
影响因子：
2.8
通讯作者：
Hazari, Nilay
中科院分区：
文献类型：
--
作者：
Guard, Louise M.;Hazari, Nilay
研究了三(2-二甲氨基乙基)胺(Me(6)tren)与格氏试剂及相关镁前驱体的反应。Me(6)tren与2当量的PhMgBr在乙醚中反应生成[(Me(6)tren)MgBr]Br(1)，其中Me(6)tren以kappa(4)形式键合。这是第一个含有Me(6)tren或相关的三(氨乙基)胺配体的镁络合物的例子。相反，当用1或2当量的Me(6)tren处理MeMgBr时，生成了含有1和烷基物种[(Me(6)tren)MgMe]Br3的混合物。Me(6)tren与大于4当量的MeMgBr反应生成[(Me(6)tren)MgBr](2)[MgBr4](4)，这是一种具有不同反离子的1的类似物。通过Me2 Mg与Me(6)tren的反应，合成了具有Kappa(3)结合Me(6)tren配体的二烷基镁化合物(Me(6)tren)MgMe2(5)。5与过量的苯乙炔或二氧化碳反应分别生成(Me(6)tren)、Mg(Ccph)(2)(6)和Mg(OAc)(2)，而与苯甲醇、苯甲胺、4-叔丁基邻苯二酚、4-叔丁基苯酚和苯胺反应均导致分解。添加1当量的2，6-叶氨酸中心点HBArF(BARF=tetrakis(3，5-bis(trifluoromethyl)phenyl)borate)至5)形成[(Me(6)Tren)MgMe]BarF(7)，这是中性辅助配体负载阳离子单烷基镁物种的罕见例子。对化合物1、4和5进行了结晶学表征。
The reaction of tris(2-dimethylaminoethyl)amine (Me(6)tren) with Grignard reagents and related Mg precursors has been investigated. Treating Me(6)tren with 2 equiv of PhMgBr in diethyl ether resulted in the formation of [(Me(6)tren)MgBr]Br (1), in which Me(6)tren is bound in a kappa(4) fashion. This is the first example of a Mg complex containing Me(6)tren or a related tris(aminoethyl)amine ligand. In contrast, when MeMgBr was treated with either 1 or 2 equiv of Me(6)tren, a mixture containing 1 and the alkyl species [(Me(6)tren)MgMe]Br (3) was produced. It was not possible to separate the two compounds to generate a pure sample of 3. Reaction between Me(6)tren and greater than 4 equiv of MeMgBr formed [(Me(6)tren)MgBr](2)[MgBr4] (4), an analogue of 1 with a different counterion. The highly unusual dialkyl Mg compound (Me(6)tren)MgMe2 (5), which features a,kappa(3)-bound Me(6)tren ligand, was synthesized through the reaction of Me2Mg with Me(6)tren. The reaction of 5 with excess phenylacetylene or carbon dioxide yielded (Me(6)tren)Mg(CCPh)(2) (6) and Mg(OAc)(2), respectively, while treatment with benzylalcohol, benzylamine, 4-tert-butylcatechol, 4-tert-butylphenol, and aniline all resulted in decomposition. The addition of 1 equiv of 2,6-lutidine center dot HBArF (BArF = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) to 5 formed [(Me(6)tren)MgMe]BArF (7), a rare example of a neutral ancillary ligand supported cationic monoalkyl Mg species. Compounds 1, 4, and 5 have been crystallographically characterized.