scholarly journals Revealing the unusual role of bases in activation/deactivation of catalytic systems: O–NHC coupling in M/NHC catalysis

2018 ◽  
Vol 9 (25) ◽  
pp. 5564-5577 ◽  
Author(s):  
Victor M. Chernyshev ◽  
Oleg V. Khazipov ◽  
Maxim A. Shevchenko ◽  
Andrey Yu. Chernenko ◽  
Alexander V. Astakhov ◽  
...  

Usual oxygen bases decompose M/NHC complexes to give “NHC-free” metal species and azolones.

2016 ◽  
Vol 10 (3) ◽  
pp. 259-270
Author(s):  
Ludmila Matienko ◽  
◽  
Larisa Mosolova ◽  
Vladimir Binyukov ◽  
Gennady Zaikov ◽  
...  

Mechanism of catalysis with binary and triple catalytic systems based on redox inactive metal (lithium) compound {LiSt+L2} and {LiSt+L2+PhOH} (L2=DMF or HMPA), in the selective ethylbenzene oxidation by dioxygen into -phenylethyl hydroperoxide is researched. The results are compared with catalysis by nickel-lithium triple system {NiII(acac)2+LiSt+PhOH} in selective ethylbenzene oxidation to PEH. The role of H-bonding in mechanism of catalysis is discussed. The possibility of the stable supramolecular nanostructures formation on the basis of triple systems, {LiSt+L2+PhOH}, due to intermolecular H-bonds, is researched with the AFM method.


2020 ◽  
Vol 13 ◽  
Author(s):  
Kumari Jyoti ◽  
Punyasloka Pattnaik ◽  
Tej Singh

Background:: Synthesis of metallic nanoparticles has attracted extensive vitality in numerous research areas such as drug delivery, biomedicine, catalysis etc. where continuous efforts are being made by scientists and engineers to investigate new dimensions for both technological and industrial advancements. Amongst numerous metallic nanoparticles, silver nanoparticle (AgNPs) is a novel metal species with low toxicity, higher stability and significant chemical, physical and biological properties. Methods:: In this, various methods for the fabrication of AgNPs are summarized. Importantly, we concentrated on the role of reducing agents of different plants parts, various working conditions such as AgNO3 concentration; ratio of AgNO3/extract; incubation time; centrifugal conditions, size and shapes. Results:: This study suggested that eco-friendly and non toxic biomolecules present in the extracts (e.g. leaf, stem and root) of plants are used as reducing and capping agents for silver nanoparticles fabrication. This method of fabrication of silver nanoparticles using plants extracts is comparatively cost-effective and simple. A silver salt is simply reduced by biomolecules present in the extracts of these plants. In this review, we have emphasized the synthesis and antibacterial potential of silver nanoparticles using various plant extracts. Conclusion:: Fabrication of silver nanoparticles using plant extracts have advantage over the other physical methods, as it is safe, eco-friendly and simple to use. Plants have huge potential for the fabrication of silver nanoparticles of wide potential of applications with desired shape and size.


Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 39
Author(s):  
Lyudmila V. Parfenova ◽  
Pavel V. Kovyazin ◽  
Almira Kh. Bikmeeva ◽  
Eldar R. Palatov

The activity and chemoselectivity of the Cp2ZrCl2-XAlBui2 (X = H, Bui) and [Cp2ZrH2]2-ClAlEt2 catalytic systems activated by (Ph3C)[B(C6F5)4] or B(C6F5)3 were studied in reactions with 1-hexene. The activation of the systems by B(C6F5)3 resulted in the selective formation of head-to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yRnAl(C6F5)3−n were found to be the key intermediates of alkene dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers.


2018 ◽  
Vol 9 (6) ◽  
pp. 723-736 ◽  
Author(s):  
Elisa Calabrese ◽  
Pasquale Longo ◽  
Carlo Naddeo ◽  
Annaluisa Mariconda ◽  
Luigi Vertuccio ◽  
...  

PurposeThe purpose of this paper is to highlight the relevant role of the stereochemistry of two Ruthenium catalysts on the self-healing efficiency of aeronautical resins.Design/methodology/approachHere, a very detailed evaluation on the stereochemistry of two new ruthenium catalysts evidences the crucial role of the spatial orientation of phenyl groups in the N-heterocyclic carbene ligands in determining the temperature range within the curing cycles is feasible without deactivating the self-healing mechanisms (ring-opening metathesis polymerization reactions) inside the thermosetting resin. The exceptional activity and thermal stability of the HG2MesPhSyncatalyst, with the syn orientation of phenyl groups, highlight the relevant potentiality and the future perspectives of this complex for the activation of the self-healing function in aeronautical resins.FindingsThe HG2MesPhSyncomplex, with the syn orientation of the phenyl groups, is able to activate metathesis reactions within the highly reactive environment of the epoxy thermosetting resins, cured up to 180°C, while the other stereoisomer, with the anti-orientation of the phenyl groups, does not preserve its catalytic activity in these conditions.Originality/valueIn this paper, a comparison between the self-healing functionality of two catalytic systems has been performed, using metathesis tests and FTIR spectroscopy. In the field of the design of catalytic systems for self-healing structural materials, a very relevant result has been found: a slight difference in the molecular stereochemistry plays a key role in the development of self-healing materials for aeronautical and aerospace applications.


2021 ◽  
Author(s):  
Yang Gao ◽  
Sima Yazdani ◽  
Aaron Kendrick ◽  
Glen Junor ◽  
Douglas Grotjahn ◽  
...  

Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with a limited scope of substrates and/or reagents, with general solutions lacking. Herein, we describe a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes that is facilitated by strongly donating cyclic (alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl- and aryl-substituted alkynes are coupled with a variety of boryl and silyl reagents with high α-selectivity. The reaction is scalable, and the products are versatile intermediates that can participate in various downstream transformations. Preliminary mechanistic experiments shed light on the role of CAAC ligands in this process.


2020 ◽  
Vol 5 (13) ◽  
pp. 4058-4068
Author(s):  
Rusrina Salaeh ◽  
Kajornsak Faungnawakij ◽  
Nawee Kungwan ◽  
Pussana Hirunsit

Catalysts ◽  
2018 ◽  
Vol 8 (9) ◽  
pp. 365 ◽  
Author(s):  
Irina L. Simakova ◽  
Andrey V. Simakov ◽  
Dmitry Yu. Murzin

This review fills an apparent gap existing in the literature by providing an overview of the readily available terpenes and existing catalytic protocols for preparation of terpene-derived amines. To address the role of solid catalysts in amination of terpenes the same reactions with homogeneous counterparts are also discussed. Such catalysts can be considered as a benchmark, which solid catalysts should match. Although catalytic systems based on transition metal complexes have been developed for synthesis of amines to a larger extent, there is an apparent need to reduce the production costs. Subsequently, homogenous systems based on cheaper metals operating by nucleophilic substitution (e.g., Ni, Co, Cu, Fe) with a possibility of easy recycling, as well as metal nanoparticles (e.g., Pd, Au) supported on amphoteric oxides should be developed. These catalysts will allow synthesis of amine derivatives of terpenes which have a broad range of applications as specialty chemicals (e.g., pesticides, surfactants, etc.) and pharmaceuticals. The review will be useful in selection and design of appropriate solid materials with tailored properties as efficient catalysts for amination of terpenes.


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