The metalation of 1,2-bis(anilino)ethane with excess KH leads to the formation of the potassium complex [(thf)₃K₂{1,2-(PhN)₂C₂H₄}] (1). Complex 1 quantitatively reacts with anhydrous CaI₂ in THF yielding insoluble KI and dinuclear [(thf)₅Ca₂{1,2-(PhN)₂C₂H₄}₂] (2) after crystallization from a mixture of THF and hexane. Addition of N,N,N′,N′′,N′′′,N′′′-hexamethyltriethylenetetraamine (hmteta) yields [(hmteta)Ca{1,2-(PhN)₂C₂H₄}] (3). The complexes 1 and 2 proved to be inactive as catalysts in hydroamination reactions of diphenylbutadiyne with secondary amines. However, a mixture of 1 and 2 (K:Ca ratio of 2:1) mediated the addition of N-methyl-aniline and 1,2-bis(anilino)ethane to one of the C≡C triple bonds of diphenylbutadiyne. Addition of 18-crown-6 ether (18C6) leads to the formation of the sparingly soluble potassium complex [{(18C6)K}₂{1,2-(PhN)₂C₂H₄}] (5) and the insoluble calcium complex [(18C6)Ca{1,2-(PhN)₂C₂H₄}] (6). The calciate-mediated hydroamination reaction is regiocontrolled, but E- and Z-isomeric addition products are observed, regardless of whether the reaction is performed at daylight or in the dark. If toluene is used as solvent for this s-block metal-mediated hydroamination catalysis, (Z,Z)-1,4,5,8,9,12-hexaphenyl-5,8-diazadodeca-3,9-diene-1,11-diyne (Z,Z-8) precipitates, allowing isolation and characterization of this isomer. In solution, this compound isomerizes upon irradiation yielding an equilibrium between (Z,Z)-, (E,Z)- and (E,E)-isomers. The determination of the crystal structures of (Z,Z)- and (E,E)-1,4,5,8,9,12-hexaphenyl-5,8-diazadodeca-3,9-diene-1,11-diyne unequivocally allows the assignment of the NMR parameters to specific isomers.

中文翻译：

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钙和钾的1,2-双（苯胺基）乙烷配合物：合成，结构和催化活性

过量KH的1,2-双（苯胺基）乙烷金属化导致形成钾络合物[（thf）₃ K ₂ {1,2-（PhN）₂ C ₂ H ₄ }]（1）。从THF和己烷的混合物中结晶后，络合物1与无水CaI ₂在THF中定量反应，生成不溶的KI和双核[[thf）₅ Ca ₂ {1,2-（PhN）₂ C ₂ H ₄ } ₂ ]（2） 。加入Ñ，Ñ，N' ，N'' ，N'′′，N′′′-六甲基三亚乙基四胺（hmteta）产生[（hmteta）Ca {1,2-（PhN）₂ C ₂ H ₄ }]（3）。事实证明，配合物1和2在二苯基丁二炔与仲胺的加氢胺化反应中没有活性。但是，1和2的混合物（K：Ca比为2：1）介导将N-甲基苯胺和1,2-双（苯胺基）乙烷加到二苯基丁二炔的C≡C三键之一上。添加18冠6醚（18C6）导致形成难溶的钾络合物[{（18C6）K} ₂ {1,2-（PhN）₂ C₂ H ₄ }]（5）和不溶性钙络合物[（18C6）Ca {1,2-（PhN）₂ C ₂ H ₄ }]（6）。钙盐介导的加氢胺化反应是区域控制的，但是观察到E-和Z-异构加成产物，无论该反应是在白天还是在黑暗中进行。如果将甲苯用作此s嵌段金属介导的加氢胺化催化的溶剂，则（Z，Z）-1,4,5,8,9,12-六苯基-5,8-二氮杂十二烷基-3,9-二烯-1 ，11-二炔（Z，Z - 8）沉淀，从而可以分离和表征该异构体。在溶液中，该化合物在辐照下异构化，在（Z，Z）-，（E，Z）-和（E，E）异构体之间达到平衡。（Z，Z）-和（E，E）-1,4,5,8,9,12-六苯基-5,8-二氮杂十二烷基-3,9-二烯-1,11-的晶体结构的确定Diyne明确地允许将NMR参数分配给特定的异构体。