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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Heterobimetallic metallation studies of N, N-dimethylphenylethylamine (DMPEA): benzylic C-H bond cleavage/dimethylamino capture or intact DMPEA complex
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Heterobimetallic metallation studies of N, N-dimethylphenylethylamine (DMPEA): benzylic C-H bond cleavage/dimethylamino capture or intact DMPEA complex

机译：N，N-二甲基苯基乙胺（DMPEA）的异双金属金属化研究：苄基C-H键断裂/二甲基氨基捕获或完整的DMPEA复合物

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摘要

Reaction of the sodium monoamido-bisalkylzincate [(TMEDA)Na(TMP)(Bu-t)Zn(Bu-t)] (TMEDA is N, N, N', N'-tetramethylethylenediamine; TMP is 2,2,6,6-tetramethylpiperidide) and the related lithium zincate [(PMDETA) Li(TMP)Zn(Bu-t)(2)] (PMDETA is N, N, N', N '', N ''-pentamethyldiethylenetriamine) with the sensitive bio-relevant scaffold N, N-dimethylphenylethylamine, DMPEA, afforded the crystalline complexes [(TMEDA)Na(TMP)(NMe2)Zn(Bu-t)] and [(PMDETA)Li(NMe2)Zn(Bu-t)(2)], respectively, both of which have been characterized by NMR spectroscopic and X-ray crystallographic studies. Made by reaction of a LiTMP(TMP)Al(Bu-i)(2) mixture with DMPEA, a third dimethylamino-containing crystalline complex, the aluminate [(THF)Li(TMP)(NMe2)Al(Bu-i)(2)] has been similarly characterized. All three complexes can be regarded as products of cleave and capture chemistry whereby metallation at the benzylic position of DMPEA has led to a beta-elimination of an anionic Me2N fragment that has been captured by a charge balancing cationic heterobimetallic entity. While a metallated intermediate prior to the elimination has proved elusive in all of these reactions, DMPEA has been captured fully intact in the novel Lewis acid-Lewis base crystalline complex [DMPEA.Li(TMP)Zn(Me)(2)], which has also been characterized by the aforementioned techniques.
机译：单酰胺基-双烷基锌酸钠[（TMEDA）Na（TMP）（Bu-t）Zn（Bu-t）]的反应（TMEDA为N，N，N'，N'-四甲基乙二胺; TMP为2,2,6， 6-四甲基哌啶）和相关的锌酸锂[（PMDETA）Li（TMP）Zn（Bu-t）（2）]（PMDETA为N，N，N'，N''，N''-五甲基二亚乙基三胺）生物相关的支架N，N-二甲基苯基乙胺，DMPEA，得到了晶体配合物[[TMEDA] Na（TMP）（NMe2）Zn（Bu-t）]和[（PMDETA）Li（NMe2）Zn（Bu-t） 2）]，分别通过NMR光谱和X射线晶体学研究对其进行了表征。通过将LiTMP（TMP）Al（Bu-i）（2）混合物与DMPEA，第三种含二甲氨基的晶体配合物，铝酸盐[（THF）Li（TMP）（NMe2）Al（Bu-i）（ 2）]具有类似的特征。所有这三种络合物都可以视为裂解和捕获化学的产物，借此DMPEA苄基位置的金属化作用导致β-消除了阴离子Me2N片段，该片段已被电荷平衡阳离子异双金属实体捕获。尽管已证明在消除所有这些反应之前都没有消除金属化的中间体，但DMPEA已在新型路易斯酸-刘易斯碱晶体复合物[DMPEA.Li（TMP）Zn（Me）（2）]中被完整捕获。前述技术也具有特征。

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