Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
New and active earth-abundant metal catalysts are critically needed to replace precious metal-based catalysts for sustainable production of commodity and fine chemicals. We report here the design of highly robust, active, and reusable cobalt-bipyridine- and cobalt-phenanthroline-based metal–organic framework (MOF) catalysts for alkene hydrogenation and hydroboration, aldehyde/ketone hydroboration, and arene C–H borylation. In alkene hydrogenation, the MOF catalysts tolerated a variety of functional groups and displayed unprecedentedly high turnover numbers of ~2.5 × 106 and turnover frequencies of ~1.1 × 105 h–1. Structural, computational, and spectroscopic studies show that site isolation of the highly reactive (bpy)Co(THF)2 species in the MOFs prevents intermolecular deactivation and stabilizes solution-inaccessible catalysts for broad-scope organic transformations. Computational, spectroscopic, and kinetic evidence further support a hitherto unknown (bpy•–)CoI(THF)2 ground state that coordinates to alkene and dihydrogen and then undergoing σ-complex-assisted metathesis to form (bpy)Co(alkyl)(H). Reductive elimination of alkane followed by alkene binding completes the catalytic cycle. MOFs thus provide a novel platform for discovering new base-metal molecular catalysts and exhibit enormous potential in sustainable chemical catalysis.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Organization:
- NSFUNIVERSITY
- OSTI ID:
- 1247368
- Journal Information:
- Journal of the American Chemical Society, Vol. 138, Issue 9; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- ENGLISH
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