Underlying Mechanisms of Reductive Amination on Pd-Catalysts: The Unique Role of Hydroxyl Group in Generating Sterically Hindered Amine

被引：9

作者：

Hong, Zeng ^{[1
,2
]}

Ge, Xin ^{[3
]}

Zhou, Shaodong ^{[1
,2
]}

机构：

[1] Zhejiang Univ, Coll Chem & Biol Engn, Zhejiang Prov Key Lab Adv Chem Engn Manufacture T, Hangzhou 310027, Peoples R China

[2] Inst Zhejiang Univ Quzhou, 78 Jiuhua Blvd North, Quzhou 324000, Peoples R China

[3] Jiangnan Univ, Sch Chem & Mat Engn, Lihu Ave 1800, Wuxi 214122, Jiangsu, Peoples R China

来源：

INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES | 2022年 / 23卷 / 14期

基金：

中国国家自然科学基金;

关键词：

sterically hindered amine; reductive amination; competing mechanisms; in situ ATR-FTIR analysis; Pd-catalyst; ACTIVATED CARBON; PARTICLE-SIZE; HYDROGENATION; PALLADIUM; NANOPARTICLES; ADSORPTION; PHASE; PATH; ACETONITRILE; KETONES;

D O I：

10.3390/ijms23147621

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Pd nanospecies supported on porous g-C3N4 nanosheets were prepared for efficient reductive amination reactions. The structures of the catalysts were characterized via FTIR, XRD, XPS, SEM, TEM, and TG analysis, and the mechanisms were investigated using in situ ATR-FTIR spectroscopic analysis complemented by theoretical calculation. It transpired that the valence state of the Pd is not the dominating factor; rather, the hydroxyl group of the Pd(OH)(2) cluster is crucial. Thus, by passing protons between different molecules, the hydroxyl group facilitates both the generation of the imine intermediate and the reduction of the C=N unit. As a result, the sterically hindered amines can be obtained at high selectivity (>90%) at room temperature.

引用

页数：19