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Title: 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:
ORCiD logo [1];  [2]
  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; Danmarks Tekniske Univ., Lyngby (Denmark)
  2. 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. https://doi.org/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 = {2019},
month = {11}
}

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Cited by: 3 works
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