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

被引：94

作者：

Tran, Ba L. ^{[1
]}

Fulton, John L. ^{[1
]}

Linehan, John C. ^{[1
]}

Lercher, Johannes A. ^{[1
]}

Bullock, R. Morris ^{[1
]}

机构：

[1] Pacific Northwest Natl Lab, Inst Integrated Catalysis, Richland, WA 99352 USA

来源：

ACS CATALYSIS | 2018年 / 8卷 / 09期

关键词：

rhodium; nanocatalysis; arene hydrogenation; site selectivity; XAFS; N-HETEROCYCLIC CARBENES; ASYMMETRIC TRANSFER HYDROGENATION; TRANSITION-METAL NANOPARTICLES; CATALYTIC-HYDROGENATION; HETEROGENEOUS CATALYSIS; ROOM-TEMPERATURE; IONIC LIQUIDS; ARYL ETHERS; HOMOGENEOUS HYDROGENATION; RUTHENIUM NANOPARTICLES;

D O I：

10.1021/acscatal.8b02589

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：8441 / 8449

页数：17

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