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Title: Catalytic chemoselective functionalization of methane in a metal-organic framework

Abstract

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.

Authors:
ORCiD logo; ; ; ; ; ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1491812
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 1; Journal Issue: 5; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English

Citation Formats

Zhang, Xuan, Huang, Zhiyuan, Ferrandon, Magali, Yang, Dali, Robison, Lee, Li, Peng, Wang, Timothy C., Delferro, Massimiliano, and Farha, Omar K. Catalytic chemoselective functionalization of methane in a metal-organic framework. United States: N. p., 2018. Web. doi:10.1038/s41929-018-0069-6.
Zhang, Xuan, Huang, Zhiyuan, Ferrandon, Magali, Yang, Dali, Robison, Lee, Li, Peng, Wang, Timothy C., Delferro, Massimiliano, & Farha, Omar K. Catalytic chemoselective functionalization of methane in a metal-organic framework. United States. doi:10.1038/s41929-018-0069-6.
Zhang, Xuan, Huang, Zhiyuan, Ferrandon, Magali, Yang, Dali, Robison, Lee, Li, Peng, Wang, Timothy C., Delferro, Massimiliano, and Farha, Omar K. Tue . "Catalytic chemoselective functionalization of methane in a metal-organic framework". United States. doi:10.1038/s41929-018-0069-6.
@article{osti_1491812,
title = {Catalytic chemoselective functionalization of methane in a metal-organic framework},
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.},
abstractNote = {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},
journal = {Nature Catalysis},
issn = {2520-1158},
number = 5,
volume = 1,
place = {United States},
year = {2018},
month = {5}
}

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