Pd(II)-Catalyzed C═C Bond Cleavage by a Formal Group-Exchange Reaction

ACS Catalysis ◽  
2021 ◽  
pp. 8678-8683
Author(s):  
Runyou Ye ◽  
Maoshuai Zhu ◽  
Xufei Yan ◽  
Yang Long ◽  
Ying Xia ◽  
...  
Keyword(s):  
Exchange Reaction ◽  
Bond Cleavage ◽  
Formal Group

Stoichiometric CH Bond Cleavage Reaction in a Bis(carboxylato)ruthenium(II) Complex and Its Application to the Catalytic H-D Exchange Reaction of Carboxylic Acids

ChemCatChem ◽  
2013 ◽  
Vol 5 (5) ◽  
pp. 1101-1115 ◽  
Author(s):  
Masafumi Hirano ◽  
Ryo Fujimoto ◽  
Kohei Hatagami ◽  
Nobuyuki Komine ◽  
Sanshiro Komiya
Keyword(s):  
Exchange Reaction ◽  
Carboxylic Acids ◽  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction

scholarly journals Alkene-oxo and alkene-alkene coupling on Pt(II)

2005 ◽  
Author(s):  
◽  
Endre Szuromi
Keyword(s):  
Exchange Reaction ◽  
Bond Cleavage ◽  
Kinetic Studies ◽  
Direct Reaction ◽  
Triflic Acid ◽  
Common Features ◽  
Allyl Complex ◽  
Significant Discovery

Tetranuclear Pt(II) oxo-complex [(COD)4Pt4([mu]3-O)2Cl2](BF4)2 (1) (COD = 1,5- cyclooctadiene) was found to readily react with a variety of alkenes (ethylene, norbornene, propylene and cyclopentene). The most significant discovery resulted from the norbornene reaction, which gave platinaoxetane [(COD)2Pt2(OC7H10)Cl]BF4 (4), the first metallaoxetane obtained from the direct reaction of an oxo complex and an alkene. A facile alkene-exchange reaction was observed between platinaoxetane 4 and norbornene-derivative 5 giving a new platinaoxetane and free norbornene. Kinetic studies revealed that the reaction is catalyzed by possibly more than one electrophilic catalyst.We describe two probable mechanisms for the reaction.Cationic Pt(II) complexes (COD)Pt(OTf)2 and [(COD)Pt(THF)(OTf)]OTf were found to readily react with alkenes such as norbornenes, cyclopentene, propylene and ethylene.Two common features of these reactions were alkene C-H bond cleavage and triflic acid elimination. Norbornenes, cyclopentene and ethylene gave alkene-coupled products, while propylene resulted in a simple allyl complex.

Pyridyl disulfide-based thiol–disulfide exchange reaction: shaping the design of redox-responsive polymeric materials

2020 ◽  
Vol 11 (48) ◽  
pp. 7603-7624
Author(s):  
Ismail Altinbasak ◽  
Mehmet Arslan ◽  
Rana Sanyal ◽  
Amitav Sanyal
Keyword(s):  
Exchange Reaction ◽  
Functional Materials ◽  
Polymeric Materials ◽  
Disulfide Exchange ◽  
Redox Responsive ◽  
Synthetic Approaches

This review provides an overview of synthetic approaches utilized to incorporate the thiol-reactive pyridyl-disulfide motif into various polymeric materials, and briefly highlights its utilization to obtain functional materials.

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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