Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction
Abstract
Scaling relations are widely used to study surface reactions. However, the exploration of its utility in homogeneous catalysis is currently far less reported. In this work, we have investigated the transferability of the concept of scaling relations to a homogeneous catalysis reaction known as the Buchwald–Hartwig amination (BHA) reaction. The reaction of PhBr with MeNH2 using 37 different Pd–L complexes (L = phosphine ligand) is studied, and scaling relations are established among the reaction intermediates and transition states. Using the scaling relations, we construct volcano plots, which is the plot of the log(rate) vs the descriptor intermediate energy. The insights from the volcano plots agree well with the experimental trends from the literature and give direction toward better catalyst design.
- Authors:
-
[1];
- Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; Danmarks Tekniske Univ., Lyngby (Denmark)
- Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; Danmarks Tekniske Univ., Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1605368
- Grant/Contract Number:
- AC02-76SF00515; 9455
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Palladium; Group 15 compounds; Catalysts; Chemical reactions; Ligands
Citation Formats
Anand, Megha, and Nørskov, Jens K. Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction. United States: N. p., 2019.
Web. doi:10.1021/acscatal.9b04323.
Anand, Megha, & Nørskov, Jens K. Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction. United States. https://doi.org/10.1021/acscatal.9b04323
Anand, Megha, and Nørskov, Jens K. Mon .
"Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction". United States. https://doi.org/10.1021/acscatal.9b04323. https://www.osti.gov/servlets/purl/1605368.
@article{osti_1605368,
title = {Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction},
author = {Anand, Megha and Nørskov, Jens K.},
abstractNote = {Scaling relations are widely used to study surface reactions. However, the exploration of its utility in homogeneous catalysis is currently far less reported. In this work, we have investigated the transferability of the concept of scaling relations to a homogeneous catalysis reaction known as the Buchwald–Hartwig amination (BHA) reaction. The reaction of PhBr with MeNH2 using 37 different Pd–L complexes (L = phosphine ligand) is studied, and scaling relations are established among the reaction intermediates and transition states. Using the scaling relations, we construct volcano plots, which is the plot of the log(rate) vs the descriptor intermediate energy. The insights from the volcano plots agree well with the experimental trends from the literature and give direction toward better catalyst design.},
doi = {10.1021/acscatal.9b04323},
journal = {ACS Catalysis},
number = 1,
volume = 10,
place = {United States},
year = {Mon Nov 04 00:00:00 EST 2019},
month = {Mon Nov 04 00:00:00 EST 2019}
}
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