Reactions of Group 4 Metallocene Alkyne Complexes with Carbodiimides: Experimental and Theoretical Studies of the Structure and Bonding of Five-Membered Hetero-Metallacycloallenes

2011 ◽  
Vol 133 (14) ◽  
pp. 5463-5473 ◽  
Author(s):  
Katharina Kaleta ◽  
Martin Ruhmann ◽  
Oliver Theilmann ◽  
Torsten Beweries ◽  
Subhendu Roy ◽  
...  
Keyword(s):  
Theoretical Studies ◽  
Group 4 ◽  
Structure And Bonding ◽  
Alkyne Complexes ◽  
Experimental And Theoretical Studies

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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