A Domino Fusion of an Organic Ligand Depended on Metal‐Induced and Oxygen Insertion, Unraveled by Crystallography, Mass Spectrometry, and DFT Calculations. Issue 8 (14th January 2021)

• Record Type: Journal Article
• Authors: Chen, Jin‐Ming; Peng, Liang; Zhou, Fu‐Fang; Liu, Bin; Hou, Cheng; Li, Jia‐Wei; Huang, Zhou; Kurmoo, Mohamedally; Zeng, Ming‐Hua
• Is Part Of: Chemistry. Volume 27:Issue 8(2021)
• Page Start: 2875
• Page End: 2881
• Publication Date: 2021-01-14
• Subjects: cobalt-mediated reactions -- crystallography -- ESI-MS -- in situ reactions -- tetrasubstituted pyrazine; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202004396
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Herein, the reaction of (1‐methyl‐1 H ‐benzo[ d ]imidazol‐2‐yl)methanamine (L1 ) with Co(H2 O)6 Cl2, in CH3 CN 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 {[Co II 2 (3 )Cl4 ]⋅ 2 CH3 CN} (2 ), is reported. When O2 and H2 O are present, (1‐methyl‐1 H ‐benzo[ d ]imidazole‐2‐carbonyl)amide (HL1′ ) is first formed and crystallized as [Co III (L1 )2 (L1′ )]Cl2 ⋅ 2 H2 O (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 [Co II 3 (L2′′ )2 Cl4 ] 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 FeCl3 ⋅ 6 H2 O 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. Abstract : Dominoes under investigation : Tandem application of crystallography and mass spectrometry unraveled a competitive in situ domino solvothermal reaction to tetrabenzimidazol‐pyrazine within [Co2 (3 )Cl4 ] in seven steps and to a deprotonated imide anion L2′′ within 1D chain ([Co1.5 (L2′′ )] n ) in six steps.