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Title: Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction

Journal Article · · ACS Catalysis
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)
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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.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515; 9455
OSTI ID:
1605368
Journal Information:
ACS Catalysis, Vol. 10, Issue 1; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

References (55)

Recent developments in aromatic heteroatom coupling reactions journal January 1998
Scaling Relations and Kinetic Monte Carlo Simulations To Bridge the Materials Gap in Heterogeneous Catalysis journal July 2017
Beyond Scaling Relations for the Description of Catalytic Materials journal February 2019
Reactions of the 21st Century: Two Decades of Innovative Catalyst Design for Palladium-Catalyzed Cross-Couplings journal October 2015
Data Mining the C−C Cross‐Coupling Genome journal May 2019
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis journal August 2015
Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design journal June 2016
On the Generality of Molecular Volcano Plots journal February 2018
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Stereoelectronic Factors in Iron Catalysis: Synthesis and Characterization of Aryl-Substituted Iron(II) Carbonyl P–N–N–P Complexes and Their Use in the Asymmetric Transfer Hydrogenation of Ketones journal August 2011
Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination journal September 2016
Linear scaling relationships and volcano plots in homogeneous catalysis – revisiting the Suzuki reaction journal January 2015
The high-throughput highway to computational materials design journal February 2013
Guidelines for the Rational Design of Ni-Based Double Hydroxide Electrocatalysts for the Oxygen Evolution Reaction journal August 2015
Constructing Bridges between Computational Tools in Heterogeneous and Homogeneous Catalysis journal May 2018
BippyPhos: A Single Ligand With Unprecedented Scope in the Buchwald–Hartwig Amination of (Hetero)aryl Chlorides journal November 2013
Synthesis of 2-amino-2′-diphenylphosphino-1,1′-binaphthyl (MAP) and its accelerating effect on the Pd(0)-catalyzed N-arylation journal December 1998
Pd 2 dba 3 /Bippyphos: A Robust Catalyst System for the Hydroxylation of Aryl Halides with Broad Substrate Scope journal March 2013
A Highly Active Catalyst for Pd-Catalyzed Amination Reactions: Cross-Coupling Reactions Using Aryl Mesylates and the Highly Selective Monoarylation of Primary Amines Using Aryl Chlorides journal October 2008
Rational Development of Practical Catalysts for Aromatic Carbon−Nitrogen Bond Formation journal December 1998
Buchwald-Hartwig reaction: An overview journal April 2018
Assessing the reliability of calculated catalytic ammonia synthesis rates journal July 2014
Reactivity Theory of Transition-Metal Surfaces: A Brønsted−Evans−Polanyi Linear Activation Energy−Free-Energy Analysis journal December 2009
Density functional theory in surface chemistry and catalysis journal January 2011
A Generalized Picture of C–C Cross-Coupling journal July 2017
The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis journal May 2004
Palladium-catalyzed synthesis of indoles via ammonia cross-coupling–alkyne cyclization journal January 2011
[(CyPF- t Bu)PdCl 2 ]: An Air-Stable, One-Component, Highly Efficient Catalyst for Amination of Heteroaryl and Aryl Halides journal September 2008
Scaling relations between adsorption energies for computational screening and design of catalysts journal January 2014
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Brønsted−Evans−Polanyi Relation of Multistep Reactions and Volcano Curve in Heterogeneous Catalysis journal February 2008
Improving the Thermodynamic Profiles of Prospective Suzuki-Miyaura Cross-Coupling Catalysts by Altering the Electrophilic Coupling Component journal February 2018
Bulky Alkylphosphines with Neopentyl Substituents as Ligands in the Amination of Aryl Bromides and Chlorides journal June 2006
Accessing and predicting the kinetic profiles of homogeneous catalysts from volcano plots journal January 2016
Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions journal September 2016
Sequential N-Arylation of Primary Amines as a Route To Alkyldiarylamines journal August 1999
Dialkylbiaryl phosphines in Pd-catalyzed amination: a user's guide journal January 2011
Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers journal April 2015
Systematic Variation of Bidentate Ligands Used in Aryl Halide Amination. Unexpected Effects of Steric, Electronic, and Geometric Perturbations journal April 1998
A Second-Generation Catalyst for Aryl Halide Amination:  Mixed Secondary Amines from Aryl Halides and Primary Amines Catalyzed by (DPPF)PdCl 2 journal January 1996
A highly active palladium catalyst system for the arylation of anilines journal July 1998
Well-Defined N-Heterocyclic Carbenes−Palladium(II) Precatalysts for Cross-Coupling Reactions journal September 2008
An efficient, palladium-catalysed, amination of aryl bromides journal May 1999
Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces journal July 2007
Sterically Hindered Chelating Alkyl Phosphines Provide Large Rate Accelerations in Palladium-Catalyzed Amination of Aryl Iodides, Bromides, and Chlorides, and the First Amination of Aryl Tosylates journal July 1998
An Improved Catalyst System for Aromatic Carbon−Nitrogen Bond Formation:  The Possible Involvement of Bis(Phosphine) Palladium Complexes as Key Intermediates journal January 1996
Biaryl Phosphane Ligands in Palladium-Catalyzed Amination journal August 2008
Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions journal January 2009
Towards the computational design of solid catalysts journal April 2009
A P,N-Ligand for Palladium-Catalyzed Ammonia Arylation: Coupling of Deactivated Aryl Chlorides, Chemoselective Arylations, and Room Temperature Reactions journal April 2010
Room-Temperature Palladium-Catalyzed Amination of Aryl Bromides and Chlorides and Extended Scope of Aromatic C−N Bond Formation with a Commercial Ligand journal July 1999
Combining theory and experiment in electrocatalysis: Insights into materials design journal January 2017
Transmetalation, Involving Organotin Aryl, Thiolate, and Amide Compounds. An Unusual Type of Dissociative Ligand Substitution Reaction journal November 1995
A Bulky Biaryl Phosphine Ligand Allows for Palladium-Catalyzed Amidation of Five-Membered Heterocycles as Electrophiles journal March 2012
Carbon–heteroatom bond formation catalysed by organometallic complexes journal September 2008

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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