Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV)–Oxo Complex via Outer-Sphere Electron Transfer

2019 ◽  
Vol 141 (6) ◽  
pp. 2614-2622 ◽  
Author(s):  
Yong-Min Lee ◽  
Surin Kim ◽  
Kei Ohkubo ◽  
Kyung-Ha Kim ◽  
Wonwoo Nam ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Oxygen Atom ◽  
Outer Sphere ◽  
Hydrogen Atom Transfer ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Triflic Acid ◽  
Oxygen Atom Transfer ◽  
Outer Sphere Electron Transfer

The water–boryl radical as a proton-coupled electron transfer reagent for carbon dioxide, formic acid, and formaldehyde — Theoretical approach

2013 ◽  
Vol 91 (2) ◽  
pp. 155-168
Author(s):  
Waled Tantawy ◽  
Ahmed Hashem ◽  
Nabil Yousif ◽  
Eman Flefel
Keyword(s):  
Carbon Dioxide ◽  
Hydrogen Bond ◽  
Electron Transfer ◽  
Hydrogen Atom ◽  
Transfer Process ◽  
Carbonyl Compounds ◽  
Hydrogen Atom Transfer ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer

The thermochemistry of the hydrogen atom transfer reactions from the H2O–BX2 radical system (X = H, CH3, NH2, OH, F) to carbon dioxide, formic acid, and (or) formaldehyde, which produce hydroxyformyl, dihydroxymethyl, and hydroxymethyl radicals, respectively, were investigated theoretically at ROMP2/6–311+G(3DF,2P)//UB3LYP/6–31G(D) and UG3(MP2)-RAD levels of theory. Surprisingly, in the cases of a strong Lewis acid (X = H, CH3, F), the spin transfer process from the water–boryl radical to the carbonyl compounds was barrier-free and associated with a dramatic reduction in the B–H bond dissociation energy (BDE) relative to that of isolated water–borane complexes. Examining the coordinates of these reactions revealed that the entire hydrogen atom transfer process is governed by the proton-coupled electron transfer (PCET) mechanism. Hence, the elucidated mechanism has been applied in the cases of weak Lewis acids (X = NH2, OH), and the variation in the accompanied activation energy was attributed to the stereoelectronic effect interplaying in CO2 and HCOOH compared with HCHO. We ascribed the overall mechanism as a SA-induced five-center cyclic PCET, in which the proton transfers across the so-called complexation-induced hydrogen bond (CIHB) channel, while the SOMOB–LUMOC=O′ interaction is responsible for the electron migration process. Owing to previous reports that interrelate the hydrogen-bonding and the rate of proton-coupled electron-transfer reactions, we postulated that “the rate of the PCET reaction is expected to be promoted by the covalency of the hydrogen bond, and any factor that enhances this covalency could be considered an activator of the PCET process.” This postulate could be considered a good rationale for the lack of a barrier associated with the hydrogen atom transfer from the water-boryl radical system to the carbonyl compounds. Light has been shed on the water–boryl radical reagent from the thermodynamic perspective.

Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions

2015 ◽  
Vol 54 (15) ◽  
pp. 7152-7164 ◽  
Author(s):  
Mainak Mitra ◽  
Hassan Nimir ◽  
Serhiy Demeshko ◽  
Satish S. Bhat ◽  
Sergey O. Malinkin ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Oxygen Atom ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
Oxo Complexes ◽  
Pentadentate Ligands ◽  
Oxygen Atom Transfer Reactions ◽  
Atom Transfer Reactions

scholarly journals Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

2015 ◽  
Vol 6 (6) ◽  
pp. 3624-3632 ◽  
Author(s):  
Junying Chen ◽  
Heejung Yoon ◽  
Yong-Min Lee ◽  
Mi Sook Seo ◽  
Ritimukta Sarangi ◽  
...  
Keyword(s):  
Oxygen Atom ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Triflic Acid ◽  
Oxygen Atom Transfer ◽  
Oxo Complexes ◽  
Atom Transfer Reactions

Binding of two HOTf molecules to MnIV(O) species resulted in contrasting effects on the reactivities in oxygen atom transfer and H-atom transfer reactions.

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