Aryl-substituted Triarsiranes: Synthesis and Reactivity

2020 ◽  
Author(s):  
André Schumann ◽  
Jonas Bresien ◽  
Malte Fischer ◽  
Christian Hering-Junghans
Keyword(s):  
Organic Chemistry ◽  
Electronic Structure ◽  
Heterocyclic Carbenes ◽  
Synthetic Approaches ◽  
Inorganic And Organic

Cyclotriarsanes are rare and limited synthetic approaches have hampered reactivity studies on these systems. Described in here is a scalable synthetic protocol towards (AsAr)<sub>3</sub> (Ar = Dip, 2,6-<sup>i</sup>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>; Tip, 2,4,6-<sup>i</sup>Pr<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>), which allowed to study their reactivity towards [Cp<sub>2</sub>Ti(C<sub>2</sub>(SiMe<sub>3</sub>)<sub>2</sub>], affording titanocene diarsene complexes and towards N-heterocyclic carbenes (NHCs) to give straightforward access to a variety of NHC-arsinidene adducts. The electronic structure of the titanium diarsene complxes has been studied and they are best described as Ti(IV) species with a doubly reduced As<sub>2</sub>Ar<sub>2</sub> ligand. These findings will make (AsAr)<sub>3</sub> valuable precursors in the synthetic inorganic and organic chemistry.

scholarly journals Aryl-substituted Triarsiranes: Synthesis and Reactivity

2020 ◽  
Author(s):  
André Schumann ◽  
Jonas Bresien ◽  
Malte Fischer ◽  
Christian Hering-Junghans
Keyword(s):  
Organic Chemistry ◽  
Electronic Structure ◽  
Heterocyclic Carbenes ◽  
Synthetic Approaches ◽  
Inorganic And Organic

Cyclotriarsanes are rare and limited synthetic approaches have hampered reactivity studies on these systems. Described in here is a scalable synthetic protocol towards (AsAr)<sub>3</sub> (Ar = Dip, 2,6-<sup>i</sup>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>; Tip, 2,4,6-<sup>i</sup>Pr<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>), which allowed to study their reactivity towards [Cp<sub>2</sub>Ti(C<sub>2</sub>(SiMe<sub>3</sub>)<sub>2</sub>], affording titanocene diarsene complexes and towards N-heterocyclic carbenes (NHCs) to give straightforward access to a variety of NHC-arsinidene adducts. The electronic structure of the titanium diarsene complxes has been studied and they are best described as Ti(IV) species with a doubly reduced As<sub>2</sub>Ar<sub>2</sub> ligand. These findings will make (AsAr)<sub>3</sub> valuable precursors in the synthetic inorganic and organic chemistry.

scholarly journals N-Heterocyclic Carbene Catalysis under Oxidizing Conditions

Catalysts ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 549 ◽  
Author(s):  
Krzysztof Dzieszkowski ◽  
Zbigniew Rafiński
Keyword(s):  
Organic Chemistry ◽  
Biological Activity ◽  
Organic Synthesis ◽  
Heterocyclic Carbenes ◽  
Natural Product Synthesis ◽  
Cooperative Catalysis ◽  
Cyclic Compounds ◽  
Synthetic Approaches ◽  
Further Development ◽  
Vast Range

N-heterocyclic carbene organocatalysis under oxidizing conditions provides a vast range of various synthetic procedures via diverse mechanisms. The available catalysts, bases, oxidants, and oxidizing methods afford numerous opportunities for developing this branch of organocatalysis. Furthermore, implementation of tandem reactions and cooperative catalysis in the described methodology significantly expands the possibilities of modern organic chemistry. This approach allows the synthesis of different structurally complex and often enantiomerically enriched substances, which can be interesting in terms of biological activity and natural product synthesis. Many esters, amides, thioesters, lactams, lactones, and other cyclic compounds obtained in oxidative or oxygenative reactions promoted by N-heterocyclic carbenes can be interesting precursors in advanced organic synthesis. Sophistication and broad applicability prove that the described synthetic approaches are exceptionally worthy of further development.

Coumaraz-2-on-4-ylidene: Ambiphilic N-Heterocyclic Carbenes with a Tunable Electronic Structure

2018 ◽  
Vol 130 (28) ◽  
pp. 8739-8743 ◽  
Author(s):  
Hayoung Song ◽  
Hyunho Kim ◽  
Eunsung Lee
Keyword(s):  
Electronic Structure ◽  
Heterocyclic Carbenes

scholarly journals En Route to European Journals of Inorganic and Organic Chemistry

1997 ◽  
Vol 1997 (1) ◽  
pp. A1-A1
Author(s):  
Jan B. F. N. Engberts ◽  
Klaus Hafner ◽  
Henning Hopf
Keyword(s):  
Organic Chemistry ◽  
Inorganic And Organic

scholarly journals NHC Ligated Oximes: Exploring the Electronic Structure and Properties

2021 ◽  
Author(s):  
Mohammad Ovais Dar ◽  
Gurudutt Dubey ◽  
Tejender Singh ◽  
Prasad Bharatam
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Functional Group ◽  
Functional Unit ◽  
Chemical Species ◽  
Heterocyclic Carbenes ◽  
Coordination Interaction ◽  
Structure And Properties ◽  
Main Group Elements ◽  
The Past

Compounds with (NHC)→E coordination bond are being generated and their chemistry is being explored over the past 15 years (NHC= N-heterocyclic carbenes, E = main group elements). Many examples of species with N-heterocyclic olefins (NHOs) are known, which exhibit umpolung chemistry. Increasing number of chemical species, which carry NHC as a functional unit, are being reported. There is a need to understand their electronic structure. Alkylated imidazole oximes (cationic, found useful in medicinal chemistry) ((NHC)-C(H)=N-OH(+)) carry NHC unit as a functional group. Similarly, the corresponding nitroso-N-heterocyclic olefins ((NHC)=C(R)-N=O) also carry NHC as a functional unit. It is important to establish the interaction between the NHC unit and the rest part of the molecule in these species. Density functional (DFT) study has been carried out to explore the electronic structure details of a few oximes and nitroso NHOs. The results indicate that a structure with NHC→C coordination interaction can be considered as one of the resonance structures of these species.

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