Temperature-Scanning Reaction Protocol Offers Insights into Activation Parameters in the Buchwald-Hartwig Pd-Catalyzed Amination of Aryl Halides

被引：12
作者：
Schmidt, Olivia P. [1 ]
Blackmond, Donna G. [1 ]
机构：
[1] Scripps Res, Dept Chem, La Jolla, CA 92037 USA
来源：
ACS CATALYSIS | 2020年 / 10卷 / 15期
基金：
瑞士国家科学基金会; 美国国家科学基金会;
关键词：
Pd catalysis; reaction progress kinetics; Eyring equation; Arrhenius equation; temperature-scanning reactions; Buchwald-Hartwig amination; OXIDATIVE ADDITION; COMPLEXES; SOLVENTS; RATES;
D O I：
10.1021/acscatal.0c01929
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：
A temperature-scanning reaction (TSR) protocol allows deconvolution of the driving forces of concentration and temperature in a single experiment, demonstrated here for the Buchwald-Hartwig amination reaction using different amine substrates that exhibit different rate-determining steps. An Eyring analysis reveals that the observed reactivity differences between 1-hexylamine and benzophenone hydrazone are related primarily to the different contributions of activation entropy in the two cases. This TSR protocol combined with other in situ kinetic methodologies including reaction progress kinetic analysis and variable time normalization analysis provides a rapid and comprehensive mechanistic picture of complex multistep catalytic reactions.
引用
收藏
页码：8926 / 8932
页数：7
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