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:
-
- 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}
}
Web of Science
Works referenced in this record:
Recent developments in aromatic heteroatom coupling reactions
journal, January 1998
- G. Frost, Christopher; Mendonça, Paul
- Journal of the Chemical Society, Perkin Transactions 1, Issue 16
Scaling Relations and Kinetic Monte Carlo Simulations To Bridge the Materials Gap in Heterogeneous Catalysis
journal, July 2017
- Jørgensen, Mikkel; Grönbeck, Henrik
- ACS Catalysis, Vol. 7, Issue 8
Beyond Scaling Relations for the Description of Catalytic Materials
journal, February 2019
- Andersen, Mie; Levchenko, Sergey V.; Scheffler, Matthias
- ACS Catalysis, Vol. 9, Issue 4
Reactions of the 21st Century: Two Decades of Innovative Catalyst Design for Palladium-Catalyzed Cross-Couplings
journal, October 2015
- Gildner, Peter G.; Colacot, Thomas J.
- Organometallics, Vol. 34, Issue 23
Data Mining the C−C Cross‐Coupling Genome
journal, May 2019
- Sawatlon, Boodsarin; Wodrich, Matthew D.; Meyer, Benjamin
- ChemCatChem, Vol. 11, Issue 16
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis
journal, August 2015
- Medford, Andrew J.; Vojvodic, Aleksandra; Hummelshøj, Jens S.
- Journal of Catalysis, Vol. 328
Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design
journal, June 2016
- Greeley, Jeffrey
- Annual Review of Chemical and Biomolecular Engineering, Vol. 7, Issue 1
On the Generality of Molecular Volcano Plots
journal, February 2018
- Wodrich, Matthew D.; Sawatlon, Boodsarin; Busch, Michael
- ChemCatChem, Vol. 10, Issue 7
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
journal, May 2009
- Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
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
- Sues, Peter E.; Lough, Alan J.; Morris, Robert H.
- Organometallics, Vol. 30, Issue 16
Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination
journal, September 2016
- Arrechea, Pedro Luis; Buchwald, Stephen L.
- Journal of the American Chemical Society, Vol. 138, Issue 38
Linear scaling relationships and volcano plots in homogeneous catalysis – revisiting the Suzuki reaction
journal, January 2015
- Busch, Michael; Wodrich, Matthew D.; Corminboeuf, Clémence
- Chemical Science, Vol. 6, Issue 12
The high-throughput highway to computational materials design
journal, February 2013
- Curtarolo, Stefano; Hart, Gus L. W.; Nardelli, Marco Buongiorno
- Nature Materials, Vol. 12, Issue 3
Guidelines for the Rational Design of Ni-Based Double Hydroxide Electrocatalysts for the Oxygen Evolution Reaction
journal, August 2015
- Diaz-Morales, Oscar; Ledezma-Yanez, Isis; Koper, Marc T. M.
- ACS Catalysis, Vol. 5, Issue 9
Constructing Bridges between Computational Tools in Heterogeneous and Homogeneous Catalysis
journal, May 2018
- Falivene, Laura; Kozlov, Sergey M.; Cavallo, Luigi
- ACS Catalysis, Vol. 8, Issue 6
BippyPhos: A Single Ligand With Unprecedented Scope in the Buchwald–Hartwig Amination of (Hetero)aryl Chlorides
journal, November 2013
- Crawford, Sarah M.; Lavery, Christopher B.; Stradiotto, Mark
- Chemistry – A European Journal, Vol. 19, Issue 49
Synthesis of 2-amino-2′-diphenylphosphino-1,1′-binaphthyl (MAP) and its accelerating effect on the Pd(0)-catalyzed N-arylation
journal, December 1998
- Vyskočil, Štěpán; Smrčina, Martin; Kočovský, Pavel
- Tetrahedron Letters, Vol. 39, Issue 50
Pd 2 dba 3 /Bippyphos: A Robust Catalyst System for the Hydroxylation of Aryl Halides with Broad Substrate Scope
journal, March 2013
- Lavery, Christopher B.; Rotta-Loria, Nicolas L.; McDonald, Robert
- Advanced Synthesis & Catalysis, Vol. 355, Issue 5
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
- Fors, Brett P.; Watson, Donald A.; Biscoe, Mark R.
- Journal of the American Chemical Society, Vol. 130, Issue 41
Rational Development of Practical Catalysts for Aromatic Carbon−Nitrogen Bond Formation
journal, December 1998
- Wolfe, John P.; Wagaw, Seble; Marcoux, Jean-François
- Accounts of Chemical Research, Vol. 31, Issue 12
Buchwald-Hartwig reaction: An overview
journal, April 2018
- Heravi, Majid M.; Kheilkordi, Zohreh; Zadsirjan, Vahideh
- Journal of Organometallic Chemistry, Vol. 861
Assessing the reliability of calculated catalytic ammonia synthesis rates
journal, July 2014
- Medford, A. J.; Wellendorff, J.; Vojvodic, A.
- Science, Vol. 345, Issue 6193
Reactivity Theory of Transition-Metal Surfaces: A Brønsted−Evans−Polanyi Linear Activation Energy−Free-Energy Analysis
journal, December 2009
- van Santen, Rutger A.; Neurock, Matthew; Shetty, Sharan G.
- Chemical Reviews, Vol. 110, Issue 4
Density functional theory in surface chemistry and catalysis
journal, January 2011
- Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
A Generalized Picture of C–C Cross-Coupling
journal, July 2017
- Busch, Michael; Wodrich, Matthew D.; Corminboeuf, Clémence
- ACS Catalysis, Vol. 7, Issue 9
The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis
journal, May 2004
- Bligaard, T.; Nørskov, J. K.; Dahl, S.
- Journal of Catalysis, Vol. 224, Issue 1
Palladium-catalyzed synthesis of indoles via ammonia cross-coupling–alkyne cyclization
journal, January 2011
- Alsabeh, Pamela G.; Lundgren, Rylan J.; Longobardi, Lauren E.
- Chemical Communications, Vol. 47, Issue 24
[(CyPF- t Bu)PdCl 2 ]: An Air-Stable, One-Component, Highly Efficient Catalyst for Amination of Heteroaryl and Aryl Halides
journal, September 2008
- Shen, Qilong; Hartwig, John F.
- Organic Letters, Vol. 10, Issue 18
Scaling relations between adsorption energies for computational screening and design of catalysts
journal, January 2014
- Montemore, Matthew M.; Medlin, J. Will
- Catal. Sci. Technol., Vol. 4, Issue 11
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Brønsted−Evans−Polanyi Relation of Multistep Reactions and Volcano Curve in Heterogeneous Catalysis
journal, February 2008
- Cheng, Jun; Hu, P.; Ellis, Peter
- The Journal of Physical Chemistry C, Vol. 112, Issue 5
Improving the Thermodynamic Profiles of Prospective Suzuki-Miyaura Cross-Coupling Catalysts by Altering the Electrophilic Coupling Component
journal, February 2018
- Busch, Michael; Wodrich, Matthew D.; Corminboeuf, Clémence
- ChemCatChem, Vol. 10, Issue 7
Bulky Alkylphosphines with Neopentyl Substituents as Ligands in the Amination of Aryl Bromides and Chlorides
journal, June 2006
- Hill, Lensey L.; Moore, Lucas R.; Huang, Rongcai
- The Journal of Organic Chemistry, Vol. 71, Issue 14
Accessing and predicting the kinetic profiles of homogeneous catalysts from volcano plots
journal, January 2016
- Wodrich, Matthew D.; Busch, Michael; Corminboeuf, Clémence
- Chemical Science, Vol. 7, Issue 9
Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions
journal, September 2016
- Ruiz-Castillo, Paula; Buchwald, Stephen L.
- Chemical Reviews, Vol. 116, Issue 19
Sequential N-Arylation of Primary Amines as a Route To Alkyldiarylamines
journal, August 1999
- Harris, Michele C.; Geis, Oliver; Buchwald, Stephen L.
- The Journal of Organic Chemistry, Vol. 64, Issue 16
Dialkylbiaryl phosphines in Pd-catalyzed amination: a user's guide
journal, January 2011
- Surry, David S.; Buchwald, Stephen L.
- Chem. Sci., Vol. 2, Issue 1
Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers
journal, April 2015
- Calle-Vallejo, Federico; Loffreda, David; Koper, Marc T. M.
- Nature Chemistry, Vol. 7, Issue 5
Systematic Variation of Bidentate Ligands Used in Aryl Halide Amination. Unexpected Effects of Steric, Electronic, and Geometric Perturbations
journal, April 1998
- Hamann, Blake C.; Hartwig, John F.
- Journal of the American Chemical Society, Vol. 120, Issue 15
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
- Driver, Michael S.; Hartwig, John F.
- Journal of the American Chemical Society, Vol. 118, Issue 30
A highly active palladium catalyst system for the arylation of anilines
journal, July 1998
- Sadighi, Joseph P.; Harris, Michele C.; Buchwald, Stephen L.
- Tetrahedron Letters, Vol. 39, Issue 30
Well-Defined N-Heterocyclic Carbenes−Palladium(II) Precatalysts for Cross-Coupling Reactions
journal, September 2008
- Marion, Nicolas; Nolan, Steven P.
- Accounts of Chemical Research, Vol. 41, Issue 11
An efficient, palladium-catalysed, amination of aryl bromides
journal, May 1999
- Guari, Yannick; van Es, Daan S.; Reek, Joost N. H.
- Tetrahedron Letters, Vol. 40, Issue 19
Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007
- Abild-Pedersen, F.; Greeley, J.; Studt, F.
- Physical Review Letters, Vol. 99, Issue 1
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
- Hamann, Blake C.; Hartwig, John F.
- Journal of the American Chemical Society, Vol. 120, Issue 29
An Improved Catalyst System for Aromatic Carbon−Nitrogen Bond Formation: The Possible Involvement of Bis(Phosphine) Palladium Complexes as Key Intermediates
journal, January 1996
- Wolfe, John P.; Wagaw, Seble; Buchwald, Stephen L.
- Journal of the American Chemical Society, Vol. 118, Issue 30
Biaryl Phosphane Ligands in Palladium-Catalyzed Amination
journal, August 2008
- Surry, David S.; Buchwald, Stephen L.
- Angewandte Chemie International Edition, Vol. 47, Issue 34
Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions
journal, January 2009
- Birkholz (née Gensow), Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M.
- Chemical Society Reviews, Vol. 38, Issue 4
Towards the computational design of solid catalysts
journal, April 2009
- Nørskov, J.; Bligaard, T.; Rossmeisl, J.
- Nature Chemistry, Vol. 1, Issue 1, p. 37-46
A P,N-Ligand for Palladium-Catalyzed Ammonia Arylation: Coupling of Deactivated Aryl Chlorides, Chemoselective Arylations, and Room Temperature Reactions
journal, April 2010
- Lundgren, Rylan J.; Peters, Brendan D.; Alsabeh, Pamela G.
- Angewandte Chemie International Edition, Vol. 49, Issue 24
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
- Hartwig, John F.; Kawatsura, Motoi; Hauck, Sheila I.
- The Journal of Organic Chemistry, Vol. 64, Issue 15
Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017
- Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.
- Science, Vol. 355, Issue 6321
Transmetalation, Involving Organotin Aryl, Thiolate, and Amide Compounds. An Unusual Type of Dissociative Ligand Substitution Reaction
journal, November 1995
- Louie, Janis; Hartwig, John F.
- Journal of the American Chemical Society, Vol. 117, Issue 46
A Bulky Biaryl Phosphine Ligand Allows for Palladium-Catalyzed Amidation of Five-Membered Heterocycles as Electrophiles
journal, March 2012
- Su, Mingjuan; Buchwald, Stephen L.
- Angewandte Chemie International Edition, Vol. 51, Issue 19
Carbon–heteroatom bond formation catalysed by organometallic complexes
journal, September 2008
- Hartwig, John F.
- Nature, Vol. 455, Issue 7211
Works referencing / citing this record:
Surface chemistry dictates stability and oxidation state of supported single metal catalyst atoms
journal, January 2020
- Alexopoulos, Konstantinos; Vlachos, Dionisios G.
- Chemical Science, Vol. 11, Issue 6