Computational Study of Ni-Catalyzed C−H Functionalization: Factors That Control the Competition of Oxidative Addition and Radical Pathways

  • By Aude Marjolin
  • 2 August 2017

To guide the development of a more diverse set of Ni-catalyzed C−H bond functionalizations, a thorough understanding of the mechanisms, reactivity, and selectivity of these reactions is required. Peng Liu and his student Humair Omer have undertaken a computational study of the functionalization of the C−H bonds in molecules that contain the N,N-bidentate directing group with Ni catalyst and various coupling  partners, e.g. phenyl iodide (Ph−I), which has been published in the July 26, 2017 issue of the Journal of the American Chemical Society.

Giannis Mpourmpakis Lands Cover of Catalysis Science & Technology

  • By Aude Marjolin
  • 31 May 2017

Research from Giannis Mpourmpakis' group was recently featured on the inside front cover of the Royal Society of Chemistry journal, Catalysis Science & Technology. The team’s investigations into a more energy-efficient catalytic process to produce olefins--the building blocks for polymer production--could impact potential applications in diverse technology areas from green energy and sustainable chemistry to materials engineering and catalysis. 

Structure-Activity Relations in Heterogeneous Catalysis – A View from Computational Chemistry

Phillipe Sautet
Friday, March 17, 2017 - 9:30am to 10:30am

The understanding of the catalytic properties of nanoparticle catalysts and the design of optimal composition and structures demands fast methods for the calculation of adsorption energies. By exploring the adsorption of O and OR (R=OH, OOH, OCH3) adsorbates on a large range of surface sites with 9 transition metals, we propose new structure sensitive scaling relations between the adsorption energy of two adsorbates that are valid for all metals and for all surface sites.1 This opens the way for a new class of activity volcano plots where the descriptor is not an energy...

In Silico Searches for Efficient Renewable Energy Catalysts Through Chemical Compound Space

John Keith
Friday, February 3, 2017 - 11:30am to 12:30pm

This talk will provide an overview of our group’s work using both standard and atypical high-performance computational chemistry modeling to elucidate atomic scale reaction mechanisms of catalytic reactions. I will introduce our toolkit of in silico methods for accurately modeling solvating environments and realistic nanoscale architectures. I will then present how these methods can be used for predictive insights into chemical and material design. The talk will then summarize our progress in unraveling reaction mechanisms for 1) electrochemical CO2 reduction with...

Personal | Department
Department of Chemical and Petroleum Engineering, University of Pittsburgh
Ph.D., Theoretical and Computational Chemistry, University of Crete, 2006

My research expertise is interdisciplinary, blending concepts and techniques from Chemistry, Physics, Materials Science and Chemical Engineering. I use theory and computation to investigate the physicochemical properties of nanomaterials with potential applications in diverse nanotechnological areas, ranging from energy generation and storage, to materials design, nanoparticle growth, magnetism, and catalysis.

In the Computer-Aided Nano and Energy Lab (C.A.N.E.LA.), led by Prof. Mpourmpakis, we use theory and computation to investigate the physicochemical properties of nanomaterials with potential applications in diverse nanotechnological areas, ranging from green energy generation and storage to materials engineering and catalysis. Our laboratory core expertise lies on "ab-initio" electronic-structure theoretical calculations. We develop structure-activity relationships and apply multiscale tools to elucidate complex chemical processes that take place on nanomaterials. Ultimately, we design novel nanostructures with increased, molecular-level precision and tailored multifunctionality. 

Most Cited Publications
  1. "SiC Nanotubes:  A Novel Material for Hydrogen Storage," Giannis Mpourmpakis and George E. Froudakis, George P. Lithoxoos and Jannis Samios, Nano Lett. 6, 1581 (2006)
  2. "Carbon Nanoscrolls:  A Promising Material for Hydrogen Storage," Giannis Mpourmpakis, Emmanuel Tylianakis, and George E. Froudakis, Nano Lett. 7, 1893 (2007)
  3. "Correlating Particle Size and Shape of Supported Ru/γ-Al2O3 Catalysts with NH3 Decomposition Activity," Ayman M. Karim, Vinay Prasad, Giannis Mpourmpakis, William W. Lonergan, Anatoly I. Frenkel, Jingguang G. Chen and Dionisios G. Vlachos, J. Am. Chem. Soc.131, 12230 (2009)
  4. "Why boron nitride nanotubes are preferable to carbon nanotubes for hydrogen storage?: An ab initio theoretical study," Giannis Mpourmpakis, George E. Froudakis, Catalysis Today 120, 341 (2007)
  5. "Stabilization of Si-based cage clusters and nanotubes by encapsulation of transition metal atoms," Antonis N Andriotis, Giannis Mpourmpakis, George E Froudakis2 and Madhu Menon, New J. Phys. 4, 78 (2002)
Recent Publications
  1. "Design of highly selective ethanol dehydration nanocatalysts for ethylene production," Natalie Austin,  Pavlo Kostetskyy  and  Giannis MpourmpakisNanoscale (2018)
  2. "Direct Catalytic Conversion of BiomassDerived Furan and Ethanol to Ethylbenzene," Ivo Teixeira, Benedict T.W. Lo, Pavlo Kostetskyy, Lin Ye, Chiu Tang, Giannis Mpourmpakis, and Shik Chi Edman Tsang, ACS Catalysis. January 16, 2018
  3. "Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping," Qi Li, Kelly J. Lambright, Michael G. Taylor, Kristin Kirschbaum, Tian-Yi Luo, Jianbo Zhao, Giannis Mpourmpakis, Soumitra Mokashi-Punekar, Nathaniel L. Rosi, and Rongchao JinJ. Am. Chem. Soc. 139, 17779 (2017)
  4. "Site-selective Substitution of Gold Atoms in the Au24(SR)20Nanocluster by Silver," Qi Li, Michael G. TaylorKristin Kirschbaum, Kelly J. LambrightXiaofan ZhuGiannis MpourmpakisRongchao JinJ Colloid Interface Sci. 505, 1202 (2017)
  5. "Computational Insights into Adsorption of C4 Hydrocarbons in Cation-Exchanged ZSM-12 Zeolites," Pavlo Kostetskyy and Giannis Mpourmpakis, Ind. Eng. Chem. Res. 56, 7062 (2017)

Oxide-metal Interfaces as Active Sites for Acid-base Catalysis: Oxidation State of Nanocatalyst Change with Decreasing Size, Conversion of Heterogeneous to Homogeneous Catalysis, Hybrid Systems

Gábor A. Somorjai
Friday, May 6, 2016 - 9:30am to 10:30am

When metal nanoparticles are placed on different mezoporous or microporous oxide supports the catalytic turnover rates and selectivities markedly change.  The charge flow between the metal and the oxide ionizes the adsorbed molecules at the oxide-metal interfaces and alters the catalytic chemistry (acid-base catalysis). 

The oxidation state of metal nanoparticles becomes less metallic and assume higher oxidation states with decreasing size.  The...

Metal Nanocatalysts, Their Synthesis and Size Dependent Covalent Bond Catalysis: Instrumentation for Characterization under Reaction Conditions

Gábor A. Somorjai
Thursday, May 5, 2016 - 5:00pm to 7:00pm

Colloidal chemistry is used to control the size, shape and composition of metal nanoparticles usually in the 1-10 nm range.  In-situ methods are used to characterize the size, structure (electronic and atomic), bonding, composition and oxidation states under reaction conditions.  These methods include sum frequency generation nonlinear optical spectroscopy (SFG), ambient pressure X-ray photoelectron spectroscopy (APXPS) and high pressure scanning tunneling...

Personal | Department
Department of Chemistry, University of Pittsburgh
Ph.D., Computational Organic Chemistry, University of California, 2010

Reactivity and Selectivity Rules in Organic and Organometallic Reactions
We are developing computational models to quantitatively describe the origins of reactivity and selectivity in organocatalytic and transition metal-catalyzed reactions. We perform quantum mechanical calculations to explore the reaction mechanism, followed by thorough analysis on various stereoelectronic effects to predict how changes of the catalyst structure, substituents, and solvent affect rate and selectivity. We use quantitative energy decomposition methods to dissect the key interactions in the transition state and provide chemically meaningful interpretation to the computed reactivity and selectivity. We apply these computational studies to a broad range of organic and organometallic reactions, such as C–H and C–C bond activations, coupling reactions, olefin metathesis, and polymerization reactions. 

Catalyst Screening and Prediction
We are developing a multi-scale computational screening protocol which could efficiently rank the catalysts based on ligand-substrate interaction energies in the transition state. 

Applications of Computational Chemistry in Understanding Organic Chemistry
We are collaborating with experimental groups at Pitt and many other institutions to solve problems in organic chemistry using computational methods and programs. Our goal is to establish the most effective strategy to use modern computational methods and hardware to help address the grand challenges in synthetic chemistry. 


Most Cited Publications
  1. ​​​​"Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions," Gavin O. Jones, Peng Liu, K. N. Houk and Stephen L. Buchwald, J. Am. Chem. Soc. 132, 6205 (2010)
  2. "Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies," Kyle W. Quasdorf, Aurora Antoft-Finch, Peng Liu, Amanda L. Silberstein, Anna Komaromi, Tom Blackburn, Stephen D. Ramgren, K. N. Houk, Victor Snieckus, and Neil K. Garg, J. Am. Chem. Soc. 133, 6352 (2011)
  3. "Palladium-Catalyzed Meta-Selective C–H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity," Yun-Fang Yang, Gui-Juan Cheng, Peng Liu, Dasheng Leow, Tian-Yu Sun, Ping Chen, Xinhao Zhang, Jin-Quan Yu, Yun-Dong Wu, and K. N. Houk, J. Am. Chem. Soc. 136, 344 (2014)
  4. "Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity," Peng Liu, Xiufang Xu, Xiaofei Dong, Benjamin K. Keitz, Myles B. Herbert, Robert H. Grubbs, and K. N. Houk, J. Am. Chem. Soc. 134, 1464 (2012)
  5. "Conversion of amides to esters by the nickel-catalysed activation of amide C–N bonds," Liana Hie, Noah F. Fine Nathel, Tejas K. Shah, Emma L. Baker, Xin Hong, Yun-Fang Yang, Peng Liu, K. N. Houk& Neil K. Garg, Nature, 524, 79 (2015)
Recent Publications
  1. Glycosyl Cross-Coupling of Anomeric Nucleophiles: Scope, Mechanism, and Applications in the Synthesis of Aryl C-Glycosides", Feng Zhu, Jacob Rodriguez, Tianyi Yang, Ilia Kevlishvili, Eric Miller, Duk Yi, Sloane O’Neill, Michael J. Rourke, Peng Liu, and Maciej A. Walczak, J. Am. Chem. Soc 139, 17908 (2017)
  2. "Predictive Model for Oxidative C−H Bond Functionalization Reactivity with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)", Cristian Morales-Rivera, Paul E. Floreancig, and Peng LiuJ. Am. Chem. Soc 139, 17935 (2017)
  3. "Ligand–Substrate Dispersion Facilitates the Copper-Catalyzed Hydroamination of Unactivated Olefins", Gang Lu, Richard Y. Liu, Yang Yang, Cheng Fang, Daniel S. Lambrecht, Stephen L. Buchwald, and Peng Liu, J. Am. Chem. Soc 139, 16548 (2017)
  4. "Computationally Guided Catalyst Design in the Type I Dynamic Kinetic Asymmetric Pauson−Khand Reaction of Allenyl Acetates," Lauren C. Burrows, Luke T. Jesikiewicz, Gang Lu, Steven J. Geib, Peng Liu, and Kay M. Brummond, J. Am. Chem. Soc 139, 15022 (2017)
  5. "Experimental and Computational Exploration of para-Selective Silylation with a Hydrogen-Bonded Template," Arun Maji, Dr. Srimanta Guin, Sheng Feng, Amit Dahiya, Vikas Kumar Singh, Peng Liu and  Debabrata Maiti, Angewandte Chemie International Edition, 47,14903 (2017)
Personal | Department
Department of Chemical and Petroleum Engineering, University of Pittsburgh
Ph.D., Chemical Engineering, Cornell University, 1992

The Johnson group tackles fundamental problems over a wide range of subject areas using state-of-the-art atomistic modeling methods. Current projects include CO2 capture through the following methods:

  • Selective adsorption in metal organic frameworks (MOFs).
  • Catalytic nanoparticles on amorphous supports.
  • Multiscale modeling proton-exchange membrane (PEM) based fuel cells.  
  • Hydrogen storage in metal hydrides.
  • Absorption into ionic liquids, including ionic liquids that react chemically with CO2.
  • Physical absorption of CO2 into liquid sorbents.
  • Chemical capture involving carbamate forming amines.
  • Solid-state reactions involving carbonates and bicarbonates.

Tools we use in our studies include Kohn-Sham density functional theory, first principles quantum mechanics methods, classical equilibrium and non-equilibrium molecular dynamics, and Monte Carlo simulation techniques.

Most Cited Publications
  1. "The Lennard-Jones equation of state revisited," J. Karl Johnson, John A. Zollweg & Keith E. Gubbins, Molecular Physics 78, 591 (1993)
  2. "Microporous Metal Organic Materials:  Promising Candidates as Sorbents for Hydrogen Storage," Long Pan, Michelle B. Sander, Xiaoying Huang, Jing Li, Milton Smith, Edward Bittner, Bradley Bockrath, and J. Karl JohnsonJ. Am. Chem. Soc. 126, 1308 (2004)
  3. "Molecular simulation of hydrogen adsorption in single-walled carbon nanotubes and idealized carbon slit pores," Qinyu Wang and J. Karl JohnsonJ. Chem. Phys. 110, 577 (1999)
  4. "Rapid Transport of Gases in Carbon Nanotubes," Anastasios I. Skoulidas, David M. Ackerman, J. Karl Johnson, and David S. Sholl, Phys. Rev. Lett. 89, 185901 (2002)
  5. "Adsorption of Gases in Metal Organic Materials:  Comparison of Simulations and Experiments," Giovanni Garberoglio, Anastasios I. Skoulidas, and J. Karl JohnsonJ. Phys. Chem. B 109, 13094 (2005)
Recent Publications
  1. "Adsorption and Diffusion of Fluids in Defective Carbon Nanotubes: Insights from Molecular Simulations," Benjamin J. Bucior, German V. Kolmakov, JoAnna M. Male, Jinchen Liu, De-Li Chen, Prashant Kumar, and J. Karl Johnson,  Langmuir 2017
  2. "Facile anhydrous proton transport on hydroxyl functionalized graphane," Abhishek Bagusetty, Pabitra Choudhury, Wisssam A. Saidi, Bridget Derksen, Elizabeth Gatto, and J. Karl JohnsonPhys. Rev. Lett. 118, 186101 (2017
  3. "A comparison of the correlation functions of the Lennard–Jones fluid for the first-order Duh–Haymet–Henderson closure with molecular simulations," J. Karl Johnson, Douglas Henderson, Stanislav Labík, and Anatol Malijevský, Molecular Physics (published online)
  4. "Impact of Support Interactions for Single-Atom Molybdenum Catalysts on Amorphous Silica," Christopher S. Ewing, Abhishek Bagusetty, Evan G. Patriarca, Daniel S. Lambrecht, Götz Veser, and J. Karl JohnsonInd. Eng. Chem. Res. 55, 12350 (2016)
  5. "Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports," Christopher S. Ewing, Götz Veser, Joseph J. McCarthy, Daniel S. Lambrecht, J. Karl JohnsonSurface Science 652, 278 (2016)
  6. "Cavity correlation and bridge functions at high density and near the critical point: a test of second-order Percus–Yevick theory," Austin R. Saeger, J. Karl Johnson, Walter G. Chapman & Douglas Henderson, Molecular Physics 114, 2516 (2016)