Redox catalysis involving substrate photooxidation with catalyst regeneration by substrate reduction. Simultaneous oxidative C-H bond cleavage and reductive C-S bond cleavage in thioethers catalyzed by polyoxotungstate, W10O324-

1990 ◽  
Vol 112 (23) ◽  
pp. 8427-8433 ◽  
Author(s):  
R. Carlisle Chambers ◽  
Craig L. Hill
Keyword(s):  
Bond Cleavage ◽  
Catalyst Regeneration ◽  
Redox Catalysis ◽  
Substrate Reduction

scholarly journals Analyzing Mechanisms in Co(I) Redox Catalysis Using a Pattern Recognition Platform

2020 ◽  
Author(s):  
Tianhua Tang ◽  
Christopher Sandford ◽  
Shelley D. Minteer ◽  
Matthew Sigman
Keyword(s):  
Pattern Recognition ◽  
Bond Cleavage ◽  
Linear Regression Analysis ◽  
Benzyl Bromide ◽  
Kinetic Studies ◽  
Outer Sphere ◽  
Redox Catalysis ◽  
Tridentate Ligands ◽  
Electron Transfer Mechanism ◽  
Multivariable Linear Regression Analysis

Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis. Despite the benefits brought by redox catalysis, establishing the precise nature of substrate activation remains challenging. Herein, we determine that a Co(I) complex bearing two <i>N</i>,<i>N</i>,<i>N</i>-tridentate ligands acts as a competent redox catalyst for the reduction of benzyl bromide substrates. Kinetic studies combining electroanalytical techniques with multivariable linear-regression analysis were conducted, disclosing an outer-sphere electron-transfer mechanism, which occurs in concert with C–Br bond cleavage. Furthermore, we apply a pattern recognition platform to distinguish between mechanisms in the activation of benzyl bromides, found to be dependent on the ligation state of the cobalt(I) center and ligand used.

Oligosilanes as Silyl Radical Precursors through Oxidative Si−Si Bond Cleavage Using Redox Catalysis

2020 ◽  
Vol 60 (2) ◽  
pp. 675-679 ◽  
Author(s):  
Xiaoye Yu ◽  
Maximilian Lübbesmeyer ◽  
Armido Studer
Keyword(s):  
Bond Cleavage ◽  
Redox Catalysis ◽  
Silyl Radical

Oligosilanes as Silyl Radical Precursors through Oxidative Si−Si Bond Cleavage Using Redox Catalysis

2020 ◽  
Vol 133 (2) ◽  
pp. 685-689
Author(s):  
Xiaoye Yu ◽  
Maximilian Lübbesmeyer ◽  
Armido Studer
Keyword(s):  
Bond Cleavage ◽  
Redox Catalysis ◽  
Silyl Radical

scholarly journals Analyzing Mechanisms in Co(I) Redox Catalysis Using a Pattern Recognition Platform

2020 ◽  
Author(s):  
Tianhua Tang ◽  
Christopher Sandford ◽  
Shelley D. Minteer ◽  
Matthew Sigman
Keyword(s):  
Pattern Recognition ◽  
Bond Cleavage ◽  
Linear Regression Analysis ◽  
Benzyl Bromide ◽  
Kinetic Studies ◽  
Outer Sphere ◽  
Redox Catalysis ◽  
Tridentate Ligands ◽  
Electron Transfer Mechanism ◽  
Multivariable Linear Regression Analysis

Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis. Despite the benefits brought by redox catalysis, establishing the precise nature of substrate activation remains challenging. Herein, we determine that a Co(I) complex bearing two <i>N</i>,<i>N</i>,<i>N</i>-tridentate ligands acts as a competent redox catalyst for the reduction of benzyl bromide substrates. Kinetic studies combining electroanalytical techniques with multivariable linear-regression analysis were conducted, disclosing an outer-sphere electron-transfer mechanism, which occurs in concert with C–Br bond cleavage. Furthermore, we apply a pattern recognition platform to distinguish between mechanisms in the activation of benzyl bromides, found to be dependent on the ligation state of the cobalt(I) center and ligand used.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

Oxygen-Oxygen Bond Cleavage and Formation in Co(II) Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical

2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron
Keyword(s):  
Bond Cleavage ◽  
Peroxo Complex ◽  
Oxygen Oxygen ◽  
O2 Reduction ◽  
Oxygen Bond ◽  
Pentadentate Ligand

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.

Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  
Keyword(s):  
Ammonia Synthesis ◽  
Bond Cleavage ◽  
Synthesis Process ◽  
Strong Electron ◽  
Mild Conditions ◽  
Ru Nanoparticles ◽  
Rate Determining Step ◽  
Highly Active ◽  
Composite Oxides ◽  
Low Crystalline

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>

Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  
Keyword(s):  
Ammonia Synthesis ◽  
Bond Cleavage ◽  
Synthesis Process ◽  
Strong Electron ◽  
Mild Conditions ◽  
Ru Nanoparticles ◽  
Rate Determining Step ◽  
Highly Active ◽  
Composite Oxides ◽  
Low Crystalline

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>

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