Conversion of Carbon Dioxide to Methanol Using a C-H Activated Bis(imino)pyridine Molybdenum Hydroboration Catalyst.
作者： Raja Pal , Thomas L. Groy , Ryan J. Trovitch
DOI: 10.1021/ACS.INORGCHEM.5B01102
关键词: Methanol 、 Organic chemistry 、 Methylene 、 Medicinal chemistry 、 Pyridine 、 Catalysis 、 Hydroboration 、 Imine 、 Chemistry 、 Substituent 、 Diimine
摘要: Using a multistep synthetic pathway, bis(imino)pyridine (or pyridine diimine, PDI) molybdenum catalyst for the selective conversion of carbon dioxide into methanol has been developed. Starting from (Ph2PPrPDI)Mo(CO), I2 addition afforded [(Ph2PPrPDI)MoI(CO)][I], which features seven-coordinate Mo(II) center. Heating this complex to 100 °C under vacuum resulted in CO loss and formation [(Ph2PPrPDI)MoI][I]. Reduction [(Ph2PPrPDI)MoI][I] presence excess K/Hg yielded (κ6-P,N,N,N,C,P-Ph2PPrPDI)MoH following methylene group C–H activation at α-position one PDI imine substituent. The CO2 facile insertion generate respective η1-formate complex, (κ6-P,N,N,N,C,P-Ph2PPrPDI)Mo(OCOH). When low pressures were added solutions containing pinacolborane, H3COBPin O(BPin)2 was observed along with precatalyst regeneration. HBPin limited, H2C(OBPin)2 ...
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