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: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Kuntal
authors: K
authors: Manna
authors: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Pengfei
authors: P
authors: Ji
authors: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Zekai
authors: Z
authors: Lin
authors: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Francis X
authors: FX
authors: Greene
authors: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Ania
authors: A
authors: Urban
authors: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Nathan C
authors: NC
authors: Thacker
authors: Department of Chemistry, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, USA.
authors: Wenbin
authors: W
authors: Lin