Rh(CAAC)-Catalyzed Arene Hydrogenation: Evidence for Nanocatalysis and Sterically Controlled Site-Selective Hydrogenation

We report the arene hydrogenation of ethers, amides, and esters at room temperature and low hydrogen pressure, starting from [(CAAC)­Rh­(COD)­Cl] (CAAC = cyclic alkyl amino carbene). Kinetic, mechanistic, and Rh K-edge XAFS studies showed formation of Rh nanoparticles from [(CAAC)­Rh­(COD)­Cl], in c...

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Bibliographic Details
Published in:ACS catalysis 2018-09, Vol.8 (9), p.8441-8449
Main Authors: Tran, Ba L, Fulton, John L, Linehan, John C, Lercher, Johannes A, Bullock, R. Morris
Format: Article
Language:English
Subjects:
arene
hydrogenation
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
nanoparticle
site selectivity
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Summary:We report the arene hydrogenation of ethers, amides, and esters at room temperature and low hydrogen pressure, starting from [(CAAC)­Rh­(COD)­Cl] (CAAC = cyclic alkyl amino carbene). Kinetic, mechanistic, and Rh K-edge XAFS studies showed formation of Rh nanoparticles from [(CAAC)­Rh­(COD)­Cl], in contrast to a previous report of [(CAAC)­Rh­(COD)­Cl] functioning as a homogeneous catalyst for arene hydrogenation. We determined that the site-selective arene hydrogenation catalyzed by this system is under steric control, as shown by detailed competition experiments with derivatives of ethers, amides, and esters bearing different aromatic rings of varying electronic and steric influence. This work illustrates the potential of CAAC ligands in the formation and stabilization of a colloidal dispersion of stable nanoparticle catalysts.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.8b02589