Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2022, Issue 10, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.202101019
Keywords
Metal-organic frameworks; Heterogeneous catalysis; Cobalt; Borylation; Phosphine
Categories
Funding
- CSIR-HRDG [01(3040)/21/EMR-II]
- IRD, IIT Delhi [MI02099]
- CSIR
- UGC
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A metal-organic framework supported monoligated phosphine-cobalt complex has been developed as an active heterogeneous catalyst for aromatic C-H borylation and alkene hydroboration. The catalyst shows broad substrate scope and excellent functional group tolerance, leading to the synthesis of arene- and alkyl-boronate esters with high yields and selectivity. Notably, the catalyst exhibits high turnover number and can be recycled and reused multiple times.
We report a metal-organic framework (MOF) supported monoligated phosphine-cobalt complex, which is an active heterogeneous catalyst for aromatic C-H borylation and alkene hydroboration. The mono(phosphine)-Co catalyst (MOF-P-Co) was prepared by metalation of a porous triarylphosphine-functionalized MOF (MOF-P) with CoCl2 followed by activation with NaEt3BH. The MOF catalyst has a broad substrate scope with excellent functional group tolerance to afford arene- and alkyl-boronate esters in excellent yields and selectivity. MOF-P-Co gave a turnover number (TON) of 30,000 and could be recycled and reused at least 13 times in arene C-H borylation. Importantly, the attempt to prepare the homogeneous control (Ph3P-Co) using triphenylphosphine was unsuccessful due to the facile disproportionation reactions or intermolecular ligand exchanges in the solution. In contrast, the site isolation of the active mono(phosphine)-Co species within the MOF affords the robust and coordinatively unsaturated metal complexes, allowing to explore their catalytic properties and the reaction mechanism.
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