Reporter: Sun Beiqi Supervisor: Prof. Mo Date: 4/8/2016

1. Reporter: Sun Beiqi Supervisor: Prof. Mo Date: 4/8/2016

2. Outline 1. Introduction 2. Reaction 3. Mechanism 4. Synthetic Route 5.Results

3. Introduction

4. Introduction • The development of practical catalytic systems that would employ methane as C1-source for synthetic purposes constitutes one of the challenges of modern chemistry. • There are only a few catalytic systems that have been described for the chemical transformation of methane into functionalized products in the homogeneous phase

5. Introduction

6. Reaction Create carbene, dissolve in scCO2 C-C bond formed Cheap relatively EDA supercritical carbon dioxide (scCO2) as the reaction medium Dissolve CH4 C1-source The combination of fluorine and bromine substituents in a ligand could improve the solubility of its complexes in scCO2.

7. Mechanism

8. Synthetic Route • The mixture was heated with slow stirring under nitrogen at 140 °C for 1 h allowing the gases to leave the' reactor. After that time, the temperature was raised to 170 °C and the reactor was closed

9. Synthetic Route 2 3

10. Results The reaction was performed with a 1:50 ratio of the catalyst precursor (0.005 mmol of 2 or 3) and EDA (0.25 mmol) in a mixture of carbon dioxide (90 atm) and methane (160 atm), at 40 °C. Catalyst 2 yield: 4% with respect to initial EDA,96% of initial EDA was converted into a mixture of diethyl fumarate and maleate Maybe metal-catalyzed carbene coupling. It can be minimized by maintaining a low concentration in the reaction mixture, but the pressure is too high to permit

11. Results • For copper-based catalysts, barriers are higher than those calculated for the silver counterpart

12. Results

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