A Domino Fusion of an Organic Ligand Depended on Metal-Induced and Oxygen Insertion, Unraveled by Crystallography, Mass Spectrometry, and DFT Calculations.
Jin-Ming ChenLiang PengFu-Fang ZhouBin LiuCheng HouJia-Wei LiZhou HuangMohamedally KurmooMing-Hua ZengPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2021)
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 {[CoII 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 [CoIII (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 [CoII 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.
Keyphrases
- mass spectrometry
- density functional theory
- liquid chromatography
- gas chromatography
- ms ms
- room temperature
- molecular dynamics
- molecular dynamics simulations
- capillary electrophoresis
- lymph node metastasis
- high resolution
- molecular docking
- high performance liquid chromatography
- human health
- health risk
- multiple sclerosis
- gene expression
- high glucose
- health risk assessment
- nitric oxide
- oxidative stress
- tandem mass spectrometry
- electron transfer
- diabetic rats
- climate change
- heavy metals
- crystal structure
- visible light
- solid phase extraction
- amino acid