Title
Using Computational Methods to Study Photocatalysis and Copper-Catalysis in Reactions with CF3I
Presentation Type
Presentation
Start Date
27-4-2019 10:50 AM
End Date
27-4-2019 11:29 AM
Abstract
Using Computational Methods to Study Photocatalysis and Copper-Catalysis in Reactions with CF3I
Kelsey Orzel, Natasia Fernandez, Henk Eshuis, Montclair State University
Light-driven catalysis is a promising area of chemistry. Here we study a two-part mechanism proposed by Ye and Sanford in “Merging Visible-Light Photocatalysis and Transition-Metal Catalysis in the Copper-Catalyzed Trifluoromethylation of Boronic Acids with CF3I” involving photocatalysis combined with copper catalysis as a promising example of such chemical reactions. The excited photocatalyst Ru(bpy)32+ gains an electron upon interaction with the Cu(II) complex. Ru(bpy)3+ then interacts with CF3I to produce CF3, and is regenerated as Ru(bpy)32+ after passing an electron to the Iodine. In a second step, the CF3· then reacts with CuII(OAc)2 to form (OAc)2CuII-CF3 which in turn reacts with an arylboronic acid to produce a phenyl copper complex. This complex generates an organic product and the original CuIOAc catalyst. In order to test this mechanism pathway and study the energy changes, computational studies have been done using the programs TURBOMOLE and ORCA. Calculations involving the excited states of the Ru(bpy)32+ molecule have been analyzed to determine the most significant contributing orbitals involved, and to get insight into the energies at which the molecules lie. To determine the reaction pathway of the copper-catalyzed part of the mechanism reaction energies and barriers have been obtained using DFT. If this mechanism proves to be the likely explanation for such catalysis reactions, the future chemical industry could benefit from using these more available, cost-efficient catalysts.
Using Computational Methods to Study Photocatalysis and Copper-Catalysis in Reactions with CF3I
Using Computational Methods to Study Photocatalysis and Copper-Catalysis in Reactions with CF3I
Kelsey Orzel, Natasia Fernandez, Henk Eshuis, Montclair State University
Light-driven catalysis is a promising area of chemistry. Here we study a two-part mechanism proposed by Ye and Sanford in “Merging Visible-Light Photocatalysis and Transition-Metal Catalysis in the Copper-Catalyzed Trifluoromethylation of Boronic Acids with CF3I” involving photocatalysis combined with copper catalysis as a promising example of such chemical reactions. The excited photocatalyst Ru(bpy)32+ gains an electron upon interaction with the Cu(II) complex. Ru(bpy)3+ then interacts with CF3I to produce CF3, and is regenerated as Ru(bpy)32+ after passing an electron to the Iodine. In a second step, the CF3· then reacts with CuII(OAc)2 to form (OAc)2CuII-CF3 which in turn reacts with an arylboronic acid to produce a phenyl copper complex. This complex generates an organic product and the original CuIOAc catalyst. In order to test this mechanism pathway and study the energy changes, computational studies have been done using the programs TURBOMOLE and ORCA. Calculations involving the excited states of the Ru(bpy)32+ molecule have been analyzed to determine the most significant contributing orbitals involved, and to get insight into the energies at which the molecules lie. To determine the reaction pathway of the copper-catalyzed part of the mechanism reaction energies and barriers have been obtained using DFT. If this mechanism proves to be the likely explanation for such catalysis reactions, the future chemical industry could benefit from using these more available, cost-efficient catalysts.