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Title: Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

Abstract

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1330241
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature Communications; Journal Volume: 7; Journal Issue: 2016
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Manna, Kuntal, Ji, Pengfei, Lin, Zekai, Greene, Francis X., Urban, Ania, Thacker, Nathan C., and Lin, Wenbin. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes. United States: N. p., 2016. Web. doi:10.1038/ncomms12610.
Manna, Kuntal, Ji, Pengfei, Lin, Zekai, Greene, Francis X., Urban, Ania, Thacker, Nathan C., & Lin, Wenbin. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes. United States. doi:10.1038/ncomms12610.
Manna, Kuntal, Ji, Pengfei, Lin, Zekai, Greene, Francis X., Urban, Ania, Thacker, Nathan C., and Lin, Wenbin. Tue . "Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes". United States. doi:10.1038/ncomms12610.
@article{osti_1330241,
title = {Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes},
author = {Manna, Kuntal and Ji, Pengfei and Lin, Zekai and Greene, Francis X. and Urban, Ania and Thacker, Nathan C. and Lin, Wenbin},
abstractNote = {Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.},
doi = {10.1038/ncomms12610},
journal = {Nature Communications},
number = 2016,
volume = 7,
place = {United States},
year = {Tue Aug 30 00:00:00 EDT 2016},
month = {Tue Aug 30 00:00:00 EDT 2016}
}