Methane constitutes the largest fraction of natural gas reserves and is a low-cost abundant starting material for the synthesis of value-added chemicals and fuel. Selective catalytic functionalization of methane remains a vital goal in the chemical sciences due to its low intrinsic reactivity. Borylation has recently emerged as a promising route for the catalytic functionalization of methane. A major challenge in this regard is selective borylation towards the monoborylated product that is more active than methane and can easily lead to over-functionalization. Herein, we report a highly selective microporous metal-organic framework- supported iridium(III) catalyst for methane borylation that exhibits a chemoselectivity of > 99% (mono versus bis at 19.5% yield; turnover number = 67) for monoborylated methane, with bis(pinacolborane) as the borylation reagent in dodecane, at 150 °C and 34 atm of methane, employing as little as 1.8 wt% of iridium. The preference for the monoborylated product is ascribed to the shape-selective effect of the metal-organic framework pore structures.
@article{osti_1491812,
author = {Zhang, Xuan and Huang, Zhiyuan and Ferrandon, Magali and Yang, Dali and Robison, Lee and Li, Peng and Wang, Timothy C. and Delferro, Massimiliano and Farha, Omar K.},
title = {Catalytic chemoselective functionalization of methane in a metal-organic framework},
annote = {Methane constitutes the largest fraction of natural gas reserves and is a low-cost abundant starting material for the synthesis of value-added chemicals and fuel. Selective catalytic functionalization of methane remains a vital goal in the chemical sciences due to its low intrinsic reactivity. Borylation has recently emerged as a promising route for the catalytic functionalization of methane. A major challenge in this regard is selective borylation towards the monoborylated product that is more active than methane and can easily lead to over-functionalization. Herein, we report a highly selective microporous metal-organic framework- supported iridium(III) catalyst for methane borylation that exhibits a chemoselectivity of > 99% (mono versus bis at 19.5% yield; turnover number = 67) for monoborylated methane, with bis(pinacolborane) as the borylation reagent in dodecane, at 150 °C and 34 atm of methane, employing as little as 1.8 wt% of iridium. The preference for the monoborylated product is ascribed to the shape-selective effect of the metal-organic framework pore structures.},
doi = {10.1038/s41929-018-0069-6},
url = {https://www.osti.gov/biblio/1491812},
journal = {Nature Catalysis},
issn = {ISSN 2520-1158},
number = {5},
volume = {1},
place = {United States},
publisher = {Springer Nature},
year = {2018},
month = {05}}
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Laboratory (ANL)
Sponsoring Organization:
USDOE Office of Science; National Science Foundation (NSF); USDOE Office of Science - Office of Basic Energy Sciences