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Spectroscopic studies of ambiphilic molecular complexes. Activation of small molecules with non-transition metal catalysis


EMSL Project ID
39979

Abstract

This project will provide fundamental insight into the catalytic activation and transformation of small molecules, e.g., H2, CO2, N2, CH4, by non-metal Lewis pairs in condensed phase environments. The approach will use a combination of experimental approaches (NMR, calorimetry, x-ray and neutron scattering analyses) coupled with computational (Density Functional Theory and Molecular Orbital) electronic structure methods to characterize the properties of bifunctional/ambiphilic catalytic molecular complexes. The fundamental insight gained from these studies will be used to develop predictive molecular-level structure-function relationships models that will enable the optimized molecular design to enhance catalytic control and selectivity in small molecule molecular transformations.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2010-10-01
End Date
2013-09-30
Status
Closed

Team

Principal Investigator

Thomas Autrey
Institution
Pacific Northwest National Laboratory

Team Members

Mahendra Yadav
Institution
Pacific Northwest National Laboratory

Arshad Aijaz
Institution
National Institute of Advanced Industrial Science and Technology (AIST)

Qiang Xu
Institution
National Institute of Advanced Industrial Science and Technology (AIST)

Katie Hore
Institution
University of Oxford

Thomas Nielsen
Institution
Aarhus University

Ping Chen
Institution
Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Rosario Cantelli
Institution
Sapienza - UniversitĂ  di Roma

Ewa Ronnebro
Institution
Pacific Northwest National Laboratory

William David
Institution
Rutherford Appleton Laboratory

Martin Jones
Institution
University of Oxford

Doinita Neiner
Institution
Pacific Northwest National Laboratory

Thomas Proffen
Institution
Los Alamos National Laboratory

Mark Bowden
Institution
Pacific Northwest National Laboratory

Abhijeet Karkamkar
Institution
Pacific Northwest National Laboratory

Bojana Ginovska
Institution
Pacific Northwest National Laboratory

Gregory Schenter
Institution
Pacific Northwest National Laboratory

Shawn Kathmann
Institution
Pacific Northwest National Laboratory

Donald Camaioni
Institution
Pacific Northwest National Laboratory

Herman Cho
Institution
Pacific Northwest National Laboratory

Nancy Hess
Institution
Environmental Molecular Sciences Laboratory

Related Publications

Autrey T, ME Bowden, and AJ Karkamkar. 2011. "Control of hydrogen release and uptake in amine borane molecular complexes: Thermodynamics of ammonia borane, ammonium borohydride, and the diammoniate of diborane." Faraday Discussions 151(0):157-169. doi:10.1039/C0FD00015A
Camaioni DM, B Ginovska-Pangovska, GK Schenter, SM Kathmann, and T Autrey. 2012. "Analysis of the Activation and Heterolytic Dissociation of H2 by Frustrated Lewis Pairs: NH3/BX3 (X = H, F, and Cl) ." Journal of Physical Chemistry A 116(26):7228-7237. doi:10.1021/jp3039829.
Karkamkar AJ, K Parab, D Neiner, TK Nielsen, HM Cho, DM Camaioni, and T Autrey. 2012. "Thermodynamic Study of Heterolytic Hydrogen Activation by Frustrated Borane-Amine Lewis Pairs." Dalton Transactions. doi:10.1039/c2dt31628e [In Press]
Nielsen TK, AJ Karkamkar, ME Bowden, F Besenbacher, TR Jensen, and T Autrey. 2013. "Methods to Stabilize and Destabilize Ammonium Borohydride." Dalton Transactions 42(3):680-687. doi:10.1039/C2DT31591B
Potter RG, DM Camaioni, M Vasiliu, and DA Dixon. 2010. "Thermochemistry of Lewis Adducts of BH3 and Nucleophilic Substitution of Triethylamine on NH3BH3 in Tetrahydrofuran." Inorganic Chemistry 49(22):10512-10521. doi:10.1021/ic101481c