Acid-promoted hydride transfer from an NADH analogue to a Cr(iii)–superoxo complex via a proton-coupled hydrogen atom transfer

2021 ◽  
Author(s):  
Tarali Devi ◽  
Yong-Min Lee ◽  
Shunichi Fukuzumi ◽  
Wonwoo Nam
Keyword(s):  
Hydrogen Atom ◽  
Radical Cation ◽  
Hydride Transfer ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Acid Proceeds

Acid-promoted hydride transfer from an NADH analogue to a Cr(iii)–superoxo complex in the presence of acid proceeds via the full formation of the NADH analogue radical cation, followed by the decay of the radical, and accompanied then by the formation of NAD+.

Selected-ion flow tube studies of reactions of the radical cation (HC3N)+• in the interstellar chemical synthesis of cyanoacetylene

1986 ◽  
Vol 64 (2) ◽  
pp. 399-403 ◽  
Author(s):  
A. Fox ◽  
A. B. Raksit ◽  
S. Dheandhanoo ◽  
D. K. Bohme
Keyword(s):  
Hydrogen Atom ◽  
Proton Transfer ◽  
Radical Cation ◽  
Covalent Bond ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Flow Tube ◽  
Ion Flow ◽  
Wide Range ◽  
Selected Ion Flow Tube

The radical cation (HC3N)+• was produced in a Selected-Ion Flow Tube (SIFT) apparatus from cyanoacetylene by electron impact and reacted at room temperature in helium buffer gas with a selection of molecules including H2, CO, HCN, CH4, H2O, O2, HC3N, C2H2, OCS, C2H4, and C4H2. The observed reactions exhibited a wide range of reactivity and a variety of pathways including charge transfer, hydrogen atom transfer, proton transfer, and association. Association reactions were observed with CO, O2, HCN, and HC3N. With the latter two molecules association was observed to proceed close to the collision limit, which is suggestive of covalent bond formation perhaps involving azine-like N—N bonds. For HC3N an equally rapid association has been observed by Buckley etal. with ICR (Ion Cyclotron Resonance) measurements at low pressures and this is suggestive of radiative association. The hydrogen atom transfer reaction of ionized cyanoacetylene with H2 is slow while similar reactions with CH4 and H2O are fast. The reaction with CO fails to transfer a proton. These results have implications for synthetic schemes for cyanoacetylene as proposed in recent models of the chemistry of interstellar gas clouds. Proton transfer was also observed to be curiously unfavourable with all other molecules having a proton affinity higher than (C3N)•. Also, hydrogen-atom transfer was inefficient with the polar molecules HCN and HC3N. These results suggest that interactions at close separations may lead to preferential alignment of the reacting ion and molecule which is not suited for proton transfer or hydrogen atom transfer.

Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(vi) complex

2015 ◽  
Vol 44 (16) ◽  
pp. 7634-7642 ◽  
Author(s):  
Sunder N. Dhuri ◽  
Yong-Min Lee ◽  
Mi Sook Seo ◽  
Jaeheung Cho ◽  
Dattaprasad D. Narulkar ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Bond Activation ◽  
Hydride Transfer ◽  
Hydrogen Atom Transfer ◽  
Transfer Mechanism ◽  
Atom Transfer ◽  
High Valent

Valuable insights into the hydride-transfer mechanism and C–H bond activation reactions by high-valent trans-dioxoruthenium(vi) species is provided.

Hydrocarbon Oxidation by Bis-μ-oxo Manganese Dimers:  Electron Transfer, Hydride Transfer, and Hydrogen Atom Transfer Mechanisms

2002 ◽  
Vol 124 (34) ◽  
pp. 10112-10123 ◽  
Author(s):  
Anna S. Larsen ◽  
Kun Wang ◽  
Mark A. Lockwood ◽  
Gordon L. Rice ◽  
Tae-Jin Won ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Hydride Transfer ◽  
Hydrogen Atom Transfer ◽  
Hydrocarbon Oxidation ◽  
Atom Transfer ◽  
Transfer Mechanisms

Efficient Reduction of Electron-Deficient Alkenes Enabled by a Photoinduced Hydrogen Atom Transfer

2020 ◽  
Author(s):  
Xacobe Cambeiro ◽  
Natalia A. Larionova ◽  
Jun Miyatake Ondozabal
Keyword(s):  
Hydrogen Atom ◽  
Aromatic Ring ◽  
Radical Cation ◽  
Electron Affinity ◽  
Functional Group ◽  
Hydrogen Atom Transfer ◽  
Computational Studies ◽  
Atom Transfer ◽  
Efficient Reduction

Direct hydrogen atom transfer from a photoredox-generated Hantzsch ester radical cation to electron-deficient alkenes has enabled the<br>development of an efficient formal hydrogenation under mild, operationally simple conditions. The HAT-driven mechanism, key to circumvent<br>the problems associated with the low electron affinity of alkenes, is supported by experimental and computational studies. The reaction is applied<br>to a variety of cinnamate derivatives and related structures, irrespective of the presence of electron-donating or electron-withdrawing<br>substituents in the aromatic ring and with good functional group compatibility.

scholarly journals Efficient Reduction of Electron-Deficient Alkenes Enabled by a Photoinduced Hydrogen Atom Transfer

2020 ◽  
Author(s):  
Xacobe Cambeiro ◽  
Natalia A. Larionova ◽  
Jun Miyatake Ondozabal
Keyword(s):  
Hydrogen Atom ◽  
Aromatic Ring ◽  
Radical Cation ◽  
Electron Affinity ◽  
Functional Group ◽  
Hydrogen Atom Transfer ◽  
Computational Studies ◽  
Atom Transfer ◽  
Efficient Reduction

Direct hydrogen atom transfer from a photoredox-generated Hantzsch ester radical cation to electron-deficient alkenes has enabled the<br>development of an efficient formal hydrogenation under mild, operationally simple conditions. The HAT-driven mechanism, key to circumvent<br>the problems associated with the low electron affinity of alkenes, is supported by experimental and computational studies. The reaction is applied<br>to a variety of cinnamate derivatives and related structures, irrespective of the presence of electron-donating or electron-withdrawing<br>substituents in the aromatic ring and with good functional group compatibility.

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