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A Domino Fusion of an Organic Ligand Depended on Metal‐Induced and Oxygen Insertion, Unraveled by Crystallography, Mass Spectrometry, and DFT Calculations
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-11-24 , DOI: 10.1002/chem.202004396
Jin‐Ming Chen 1, 2 , Liang Peng 1 , Fu‐Fang Zhou 1 , Bin Liu 2 , Cheng Hou 1, 3 , Jia‐Wei Li 2 , Zhou Huang 2 , Mohamedally Kurmoo 4 , Ming‐Hua Zeng 1, 2
Affiliation  

Herein, the reaction of (1‐methyl‐1 H‐benzo[d]imidazol‐2‐yl)methanamine (L1) with Co(H2O)6Cl2, in CH3CN at 120 °C, leading to the 2,3,5,6‐tetrakis(1‐methyl‐1 H‐benzo[d]imidazol‐2‐yl)pyrazine (3), isolated as a dimeric cluster {[CoII2(3)Cl4]2 CH3CN} (2), is reported. When O2 and H2O are present, (1‐methyl‐1 H‐benzo[d]imidazole‐2‐carbonyl)amide (HL1′) is first formed and crystallized as [CoIII(L1)2(L1′)]Cl22 H2O (4) before fusion of HL1′ with L1, giving 1‐methyl‐N‐(1‐methyl‐1 H‐benzo[d]imidazol‐2‐carbonyl)‐1 H‐benzo[d]imidazol‐2‐carboxamide (HL2′′) forming a one‐dimensional (1D) chain of [CoII3(L2′′)2Cl4]n (5). The combination of crystallography and mass spectrometry (ESI‐MS) of isolated crystals and the solutions taken from the reaction as a function time reveal seven intermediate steps leading to 2, but six steps for 5, for which a different sequence takes place. Control and isotope labeling experiments confirm the two carbonyl oxygen atoms in 5 originate from both air and water. The dependence on the metals, compared with FeCl36 H2O leading to a stable triheteroarylmethyl radical, is quite astounding, which could be attributed to the different oxidation states of the metals and coordination modes confirmed by DFT calculations. This metal and valence dependent process is a very useful way for selectively obtaining these large molecules, which are unachievable by common organic synthesis.

中文翻译:

有机配体的多米诺骨牌融合取决于金属诱导和氧的插入,通过晶体学,质谱法和DFT计算来揭示

在此,(1-甲基-1  H-苯并[ d ]咪唑-2-基)甲胺(L1)与Co(H 2 O)6 Cl 2在120°C的CH 3 CN中反应,导致-2,3,5,6-四(1-甲基- 1  H ^ -苯并[ d ]咪唑-2-基)吡嗪(3),分离为二聚簇{[CO II 23)氯4 ] 2据报道CH 3 CN}(2)。当存在O 2和H 2 O时,(1-甲基-1  H-苯并[ d]咪唑-2-羰基)酰胺(H L1' )首先形成并结晶为[CO IIIL12L1')]氯2 2小时2 O(4)之前的融合H的L1'L1,得到1-甲基-N-(1-甲基-1  H-苯并[ d ]咪唑-2-羰基)-1  H-苯并[ d ]咪唑-2-羧酰胺(H L2''),形成一维( 1D)[Co II 3L2''2 Cl 4 ]的链n 5)。分离出的晶体的晶体学和质谱分析(ESI-MS)以及从反应中提取的溶液作为函数时间的组合揭示了七个中间步骤导致2,而六个步骤则导致5,其中发生了不同的顺序。控制和同位素标记实验证实在两个羰基的氧原子5从空气和水起源。上金属的依赖性,具有的FeCl相比3 6 H 2导致稳定的三杂芳基甲基自由基的O非常惊人,这可能归因于金属的不同氧化态和DFT计算所证实的配位模式。这种依赖于金属和化合价的方法是一种非常有用的方法,用于选择性地获得这些大分子,而这是普通有机合成无法实现的。
更新日期:2020-11-24
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