First Bis(σ)‐borane Complexes of Group 6 Transition Metals: Experimental and Theoretical Studies

2019 ◽  
Vol 25 (36) ◽  
pp. 8585-8589 ◽  
Author(s):  
Carsten Lenczyk ◽  
Dipak Kumar Roy ◽  
Bijoy Ghosh ◽  
Johannes Schwarzmann ◽  
Ashwini K. Phukan ◽  
...  
2021 ◽  
Author(s):  
Yatheesh Narayana ◽  
Sandhya N. C. ◽  
H.E. Dinesh ◽  
Sridhar B. Thimmaiah ◽  
Kanchugarakoppal S. Rangappa ◽  
...  

Arduengo et al., isolated the first ‘bottleable’ carbene, the first N-heterocyclic carbene (NHC) 1,3-di(adamantyl)imidazol-2-ylidene resulted to an explosion of experimental and theoretical studies of novel NHCs being synthesized and analyzed have huge practical significance. These compounds emerged as successful ligands for coordinating transition metals, the complexes with NHC show diverse applications in the field of catalysis and organic transformation, NHC as ligand to main group elements and their properties and applications. Here this chapter provides the concise overview of N-heterocycle carbene as an organocatalyst that provides different organic transformation on to a carbonyl group. The majority of the NHC catalyzed reactions are employed in the phenomenon of reversing the electrophilic character of carbonyl carbon to nucleophilic carbon (umpolung activity) on coordination suggests benzoin, Stetter and hydroacylation reactions. Also, non-umpolung activity of bis-electrophile α,β-unsaturated acylazoliums reaction with suitable bis-nucleophiles in the organic synthesis have been studied.


2020 ◽  
Author(s):  
Thomas Louis-Goff ◽  
Huu Vinh Trinh ◽  
Eileen Chen ◽  
Arnold L. Rheingold ◽  
Christian Ehm ◽  
...  

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.


Author(s):  
Alexey V. Kavokin ◽  
Jeremy J. Baumberg ◽  
Guillaume Malpuech ◽  
Fabrice P. Laussy

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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