配体电子效应对Ni(II)-叠氮酮配合物与炔的iClick反应的影响:合成、结构、表征和动力学研究。

IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Surajit Das, Jayanta Bag, Sayan Sarkar, Anindita Das, Kuntal Pal
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引用次数: 0

摘要

报道了两种新的方形平面Ni(II)-叠氮配合物[Ni(N3)(L)]- 1-N3和2-N3的电子可变N/S/O供体配体(其中H2LOMe: (E)-2-((2-巯基苯基)亚氨基)甲基)-6-甲氧基苯酚)和H2Lt: (E)-2,4-二叔丁基-6-((2-巯基苯基)亚氨基)甲基)苯酚)的合成和表征。氮化氮配合物中的叠氮基团比自由叠氮离子具有更强的偶极性。分离得到6个1- n3 /2- n3与3种不同炔烃的[3+2]环加成偶联产物,表征为[Ni(三氮酸盐)(L)]-1 (1/ t Bu-T)配合物。在端炔衍生的三唑酸配合物中,三唑酸配体通过N1-T原子配位,呈现出(1-T2)晶体结构。对称和非对称非端炔的三唑啉产物以N2-T键结合。基于对1-T3/2-T3的变温19F核磁共振研究,提出了N1-T/ N2-T向N2-T的转化以及在特定结合模式下的稳定性作为其平衡的热控制。详细的动力学研究表明,与丙酸甲酯的反应遵循零级速率定律,而其他两个炔烃的反应则为一级速率定律。大多数情况下,缺乏电子的乙基-4,4,4-三氟丁-2-炔酸酯的反应速度总是快于二甲基丁-2-炔酸酯,而与li - Bu连接的Ni(II)-叠氮配合物与特定炔的反应速度总是快于相同的LOMe。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Influence of the Ligand's Electronic Effect on iClick Reaction of Ni(II)-Azido Complexes with Alkynes: Synthesis, Structure, Characterization, and Kinetic Studies.

The synthesis and characterization of two new square planer Ni(II)-azido complexes [Ni(N3)(L)]-1 of 1-N3 and 2-N3 using electronically varied N/S/O donor tridentate ligands (where H2LOMe: (E)-2-(((2-mercaptophenyl)imino)methyl)-6-methoxyphenol), H2Lt Bu: (E)-2,4-di-tert-butyl-6-(((2-mercaptophenyl)imino)methyl)phenol) were reported. Azido moiety in Ni-azido complexes was found as more dipolar than free azide ion. Six number of [3+2] cycloaddition coupling product of 1-N3/2-N3 and three different alkynes were isolated and well characterized as [Ni(triazolate)(L)]-1 (1/ t Bu-T) complexes. In triazolate complexes originated from terminal alkyne, the triazolate ligand was coordinated via the N1-T atom whose (1-T2) crystal structure was presented. The triazolato products of symmetrical and unsymmetrical nonterminal alkynes were isolated as N2-T mode of binding. The conversion of N1-T/N3-T to N2-T as well as the stability in a particular mode of binding was proposed as thermal control of their equilibrium based on the variable temperature 19F NMR studies on 1-T3/2-T3. The detail kinetic studies resulted that the reaction with methyl propiolate follows zero-order rate law, whereas other two alkynes showed first-order rate. Mostly, the electron-poor ethyl-4,4,4-trifluorobut-2-ynoate always react faster than dimethyl but-2-ynedioate, and Ni(II)-azido complex with Lt Bu ligated always react with a particular alkyne in a faster rate than the same of LOMe.

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来源期刊
Chemistry - An Asian Journal
Chemistry - An Asian Journal 化学-化学综合
CiteScore
7.00
自引率
2.40%
发文量
535
审稿时长
1.3 months
期刊介绍: Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).
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