Experimental and Theoretical Studies of Mechanisms in the Homogeneous Catalytic Activation of Carbon Monoxide

1981 ◽  
pp. 19-34 ◽  
Author(s):  
H. M. FEDER ◽  
J. W. RATHKE ◽  
M. J. CHEN ◽  
L. A. CURTISS
Keyword(s):  
Carbon Monoxide ◽  
Theoretical Studies ◽  
Catalytic Activation ◽  
Experimental And Theoretical Studies

Experimental and Theoretical Studies on the Reduction of CO2 to CO with Chloro(methyl)disilane Components from the Direct Process

Synlett ◽  
2017 ◽  
Vol 28 (18) ◽  
pp. 2439-2444 ◽  
Author(s):  
Frank Jensen ◽  
Troels Skrydstrup ◽  
Mathias Flinker ◽  
Sara Lopez ◽  
Dennis Nielsen ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Dft Calculations ◽  
Theoretical Studies ◽  
Direct Process ◽  
Industrial Synthesis ◽  
Reduce Carbon Dioxide ◽  
Reduction Of Co2 ◽  
Fluoride Salts ◽  
Experimental And Theoretical Studies

Three disilanes, (CH3)3SiSi(CH3)3, Cl(CH3)2SiSi(CH3)2Cl, and Cl2(CH3)SiSi(CH3)Cl2, all representing components of the Direct Process residue for the industrial synthesis of chloromethylsilanes, were evaluated for their abilities to reduce carbon dioxide to carbon monoxide upon treatment with fluoride salts. In particular, Cl(CH3)2SiSi(CH3)2Cl proved to be highly efficient upon the use of stoichiometric amounts of potassium bifluoride. DFT calculations performed on the reduction steps with (CH3)3SiSi(CH3)3 and fluorinated analogues of this disilane suggest that the previously proposed pathway involving an intermediate silacarboxylic acid is plausible.

The Stabilizing Effect of Pre-Equilibria: A Trifluoromethyl Complex as CF2 Reservoir in Catalytic Olefin Difluorocarbenation

2020 ◽  
Author(s):  
Thomas Louis-Goff ◽  
Huu Vinh Trinh ◽  
Eileen Chen ◽  
Arnold L. Rheingold ◽  
Christian Ehm ◽  
...  
Keyword(s):  
High Selectivity ◽  
Side Reactions ◽  
Theoretical Studies ◽  
Attractive Feature ◽  
Catalyst Recovery ◽  
Wide Range ◽  
Stabilizing Effect ◽  
Experimental And Theoretical Studies

A new, efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMSCF<sub>3</sub> as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In depth experimental and theoretical studies showed that the key difluorocarbene-generating step proceeds through a bismuth non-redox synchronous mechanism generating a highly reactive free CF<sub>2</sub> in an endergonic pre-equilibrium. It is the reversibility when generating the difluorocarbene that accounts for the high selectivity, while minimizing CF<sub>2</sub>-recombination side-reactions.

Strong coupling: resonant effects

2017 ◽  
Author(s):  
Alexey V. Kavokin ◽  
Jeremy J. Baumberg ◽  
Guillaume Malpuech ◽  
Fabrice P. Laussy
Keyword(s):  
Strong Coupling ◽  
Experimental Studies ◽  
Strong Coupling Regime ◽  
Theoretical Studies ◽  
Stimulated Scattering ◽  
Quantum Theories ◽  
Pump Probe ◽  
Exciton Polaritons ◽  
Linear Optical Properties ◽  
Experimental And Theoretical Studies

This chapter presents experimental studies performed on planar semiconductor microcavities in the strong-coupling regime. The first section reviews linear experiments performed in the 1990s that evidence the linear optical properties of cavity exciton-polaritons. The chapter is then focused on experimental and theoretical studies of resonantly excited microcavity emission. We mainly describe experimental configuations in which stimulated scattering was observed due to formation of a dynamical condensate of polaritons. Pump-probe and cw experiments are described in addition. Dressing of the polariton dispersion and bistability of the polariton system due to inter-condensate interactions are discussed. The semiclassical and the quantum theories of these effects are presented and their results analysed. The potential for realization of devices is also discussed.

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