scholarly journals Evidencing an inner-sphere mechanism for NHC-Au(I)-catalyzed carbene-transfer reactions from ethyl diazoacetate

2015 ◽  
Vol 11 ◽  
pp. 2254-2260 ◽  
Author(s):  
Manuel R Fructos ◽  
Juan Urbano ◽  
M Mar Díaz-Requejo ◽  
Pedro J Pérez
Keyword(s):  
Coordination Sphere ◽  
Outer Sphere ◽  
Transfer Reactions ◽  
Ethyl Diazoacetate ◽  
Inner Sphere ◽  
Carbene Transfer ◽  
Catalyzed Reactions ◽  
Sphere Mechanism ◽  
Nitrogen Evolution

Kinetic experiments based on the measurement of nitrogen evolution in the reaction of ethyl diazoacetate (N2CHCO2Et, EDA) and styrene or methanol catalyzed by the [IPrAu]+ core (IPr = 1,3-bis(diisopropylphenyl)imidazole-2-ylidene) have provided evidence that the transfer of the carbene group CHCO2Et to the substrate (styrene or methanol) takes place in the coordination sphere of Au(I) by means of an inner-sphere mechanism, in contrast to the generally accepted proposal of outer-sphere mechanisms for Au(I)-catalyzed reactions.

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

Complete Control of the Chemoselectivity in Catalytic Carbene Transfer Reactions from Ethyl Diazoacetate:  AnN-Heterocyclic Carbene−Cu System That Suppresses Diazo Coupling

2004 ◽  
Vol 126 (35) ◽  
pp. 10846-10847 ◽  
Author(s):  
Manuel R. Fructos ◽  
Tomás R. Belderrain ◽  
M. Carmen Nicasio ◽  
Steven P. Nolan ◽  
Harneet Kaur ◽  
...  
Keyword(s):  
Transfer Reactions ◽  
Complete Control ◽  
Ethyl Diazoacetate ◽  
Diazo Coupling ◽  
Carbene Transfer

A Gold Catalyst for Carbene-Transfer Reactions from Ethyl Diazoacetate

2005 ◽  
Vol 44 (33) ◽  
pp. 5284-5288 ◽  
Author(s):  
Manuel R. Fructos ◽  
Tomás R. Belderrain ◽  
Pierre de Frémont ◽  
Natalie M. Scott ◽  
Steven P. Nolan ◽  
...  
Keyword(s):  
Gold Catalyst ◽  
Transfer Reactions ◽  
Ethyl Diazoacetate ◽  
Carbene Transfer

Quantum theory of electron-transfer reactions

1996 ◽  
Author(s):  
Wolfgang Schmickler
Keyword(s):  
Electron Transfer ◽  
Outer Sphere ◽  
Transfer Reactions ◽  
Discrete Energy ◽  
Electron Transfer Reactions ◽  
Inner Sphere ◽  
Oppenheimer Approximation ◽  
Semiconductor Electrode ◽  
The Masses ◽  
Molecular Vibrational Modes

The theory of electron-transfer reactions presented in Chapter 6 was mainly based on classical statistical mechanics. While this treatment is reasonable for the reorganization of the outer sphere, the inner-sphere modes must strictly be treated by quantum mechanics. It is well known from infrared spectroscopy that molecular vibrational modes possess a discrete energy spectrum, and that at room temperature the spacing of these levels is usually larger than the thermal energy kT. Therefore we will reconsider electron-transfer reactions from a quantum-mechanical viewpoint that was first advanced by Levich and Dogonadze. In this course we will rederive several of, the results of Chapter 6, show under which conditions they are valid, and obtain generalizations that account for the quantum nature of the inner-sphere modes. By necessity this chapter contains more mathematics than the others, but the calculations are not particularly difficult. Readers who are not interested in the mathematical details can turn to the summary presented in Section 6. To be specific we consider electron transfer from a reactant in a solution, such as [Fe(H2O)6]2+, to an acceptor, which may be a metal or semiconductor electrode, or another molecule. To obtain wavefunctions for the reactant in its reduced and oxidized state, we rely on the Born-Oppenheimer approximation, which is commonly used for the calculation of molecular properties. This approximation is based on the fact that the masses of the nuclei in a molecule are much larger than the electronic mass. Hence the motion of the nuclei is slow, while the electrons are fast and follow the nuclei almost instantaneously. The mathematical consequences will be described in the following. Let us denote by R the coordinates of all the nuclei involved, those of the central ion, its ligarids, and the surrounding solvation sphere, and by r the coordinates of all electrons.

scholarly journals Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents

2021 ◽  
Author(s):  
Lucie Cailler ◽  
Andrey P. Kroitor ◽  
Alexander G. Martynov ◽  
Yulia G. Gorbunova ◽  
Alexander B. Sorokin
Keyword(s):  
Transfer Reactions ◽  
Ethyl Diazoacetate ◽  
Wide Range ◽  
Carbene Transfer ◽  
Aromatic Heterocyclic

Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and...

A Gold Catalyst for Carbene-Transfer Reactions from Ethyl Diazoacetate

2005 ◽  
Vol 117 (33) ◽  
pp. 5418-5422 ◽  
Author(s):  
Manuel R. Fructos ◽  
Tomás R. Belderrain ◽  
Pierre de Frémont ◽  
Natalie M. Scott ◽  
Steven P. Nolan ◽  
...  
Keyword(s):  
Gold Catalyst ◽  
Transfer Reactions ◽  
Ethyl Diazoacetate ◽  
Carbene Transfer
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