ChemInform Abstract: Silica-Supported Cobalt(II) Tetrasulfophthalocyanine Catalyzed Aerobic Oxidation of Thiols to Disulfides under Neutral Conditions.

ChemInform ◽  
2008 ◽  
Vol 39 (37) ◽  
Author(s):  
Ahmad Shaabani ◽  
Naser Safari ◽  
Samad Shoghpour ◽  
Ali Hossein Rezayan
Keyword(s):  
Aerobic Oxidation ◽  
Neutral Conditions

Investigation of Phthalocyanine Catalysts for the Aerobic Synthesis of meso-Substituted Porphyrins

1997 ◽  
Vol 01 (04) ◽  
pp. 385-394 ◽  
Author(s):  
M. RAVIKANTH ◽  
CATALINA ACHIM ◽  
JOHN S. TYHONAS ◽  
ECKARD MÜNCK ◽  
JONATHAN S. LINDSEY
Keyword(s):  
Trifluoroacetic Acid ◽  
Room Temperature ◽  
Heterogeneous Catalysts ◽  
Mossbauer Spectroscopy ◽  
Oxidation Process ◽  
Aerobic Oxidation ◽  
Heterogeneous Reactions ◽  
High Concentration ◽  
Neutral Conditions ◽  
Homogeneous Reactions

The aerobic oxidation process for the synthesis of porphyrins, previously performed using 5 mol % p-chloranil (TCQ), 5 mol % iron(II) phthalocyanine ( FePc ) and stoichiometric amounts of O 2, has been refined using new phthalocyanine catalysts. Four phthalocyanine catalysts have been prepared, characterized by Mössbauer spectroscopy and examined for efficacy in the high concentration (0.1 M) synthesis of tetraphenylporphyrin at room temperature. Each phthalocyanine has been identified to be a μ-oxo dimer. Two catalysts are soluble (the μ-oxo dimers [(t-butyl)4 FePc ]2 O and [(n- C 6 H 13 O )4 FePc ]2 O ) and enable homogeneous reactions, while two are insoluble (the μ-oxo(1) and μ-oxo(2) dimers of FePc , ( FePc )2 O ) and give heterogeneous reactions. These four phthalocyanine compounds provide efficient catalysis at the 0.3–1 mol % level using only 1 mol % quinone or hydroquinone ( TCQ , DDQ , TCQH 2 or DDQH 2), affording ~25% yields of tetraphenylporphyrin in 60 min of oxidation. There are no discernible advantages of the homogeneous versus heterogeneous catalysts. The μ-oxo dimers are active, but FePc is inactive, at the 0.3 mol % level. The activity of the FePc sample at the 5 mol % level is attributed to residual μ-oxo dimer impurity. This aerobic oxidation process is superior to stoichiometric oxidation with TCQ or DDQ , and can be performed in the presence of BF 3· O ( Et )2, trifluoroacetic acid, or under neutral conditions.

scholarly journals Aerobic Methanol Oxidation over Unsupported Nanoporous Gold: The Influence of an Added Base

Catalysts ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 416 ◽  
Author(s):  
Anastasia Lackmann ◽  
Christoph Mahr ◽  
Andreas Rosenauer ◽  
Marcus Bäumer ◽  
Arne Wittstock
Keyword(s):  
Catalyst Surface ◽  
Aerobic Oxidation ◽  
Intermediate Formation ◽  
Active Oxygen ◽  
Nanoporous Gold ◽  
Oxidation Of Methanol ◽  
Alkaline Conditions ◽  
Activation Of Oxygen ◽  
Neutral Conditions ◽  
Effective Segregation

We studied the aerobic oxidation of methanol over nanoporous gold catalysts under neutral and alkaline conditions. We find that under neutral conditions the catalyst has an activation period of about 10 h while upon addition of a base the catalyst becomes active right away. After this activation period, however, the activity of the catalyst is in both cases similar. Moreover, the selectivity was not affected by the base. We tested different bases and found the largest effect when adding OH−. The cation, however, does not play a role. We conclude that it is OH−, which is impacting the reaction and propose a mechanism for the suppression of the activation period. While the catalytic cycle, i.e., the reaction of methanol on the catalyst surface seems unaffected, the transient adsorption of OH− onto the surface can facilitate the activation of molecular oxygen by donating electrons to the surface. Due to the intermediate formation of oxidic Ag species, an effective segregation of surface-near Ag can be induced, which increases the abundance of Ag being essential for the activation of oxygen at the surface. In this way, a more efficient pathway for the generation of active oxygen is opened, allowing the reaction to set in faster.

Silica-supported cobalt(II) tetrasulfophthalocyanine catalyzed aerobic oxidation of thiols to disulfides under neutral conditions

2008 ◽  
Vol 139 (6) ◽  
pp. 613-615 ◽  
Author(s):  
Ahmad Shaabani ◽  
Naser Safari ◽  
Samad Shoghpour ◽  
Ali Hossein Rezayan
Keyword(s):  
Aerobic Oxidation ◽  
Neutral Conditions

The design and catalytic performance of molybdenum active sites on an MCM-41 framework for the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

2019 ◽  
Vol 9 (3) ◽  
pp. 811-821 ◽  
Author(s):  
Zhao-Meng Wang ◽  
Li-Juan Liu ◽  
Bo Xiang ◽  
Yue Wang ◽  
Ya-Jing Lyu ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Active Sites ◽  
Aerobic Oxidation ◽  
Catalytic Performance ◽  
Mcm 41

The catalytic activity decreases as –(SiO)3Mo(OH)(O) > –(SiO)2Mo(O)2 > –(O)4–MoO.

A Self-Trapping, Bipolar Viologen Bromide Electrolyte for Aqueous Redox Flow Batteries

2020 ◽  
Author(s):  
wenda wu ◽  
Jian Luo ◽  
Fang Wang ◽  
Bing Yuan ◽  
Tianbiao Liu
Keyword(s):  
Redox Flow Battery ◽  
Capacity Retention ◽  
Redox Flow Batteries ◽  
Redox Electrolyte ◽  
Charge Process ◽  
Self Trapping ◽  
Flow Batteries ◽  
Total Capacity ◽  
Neutral Conditions ◽  
Low Solubility

Aqueous organic redox flow batteries (AORFBs) have become increasing attractive for scalable energy storage. However, it remains challenging to develop high voltage, powerful AORFBs because of the lack of catholytes with high redox potential. Herein, we report methyl viologen dibromide (<b>[MV]Br<sub>2</sub></b>) as a facile self-trapping, bipolar redox electrolyte material for pH neutral redox flow battery applications. The formation of the <b>[MV](Br<sub>3</sub>)<sub>2</sub></b> complex was computationally predicted and experimentally confirmed. The low solubility <b>[MV](Br<sub>3</sub>)<sub>2</sub></b> complex in the catholyte during the battery charge process not only mitigates the crossover of charged tribromide species (Br<sub>3</sub><sup>-</sup>) and addresses the toxicity concern of volatile bromine simultaneously. A 1.53 V bipolar MV/Br AORFB delivered outstanding battery performance at pH neutral conditions, specifically, 100% total capacity retention, 133 mW/cm<sup>2</sup> power density, and 60% energy efficiency at 40 mA/cm<sup>2</sup>.

Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

2019 ◽  
Author(s):  
Tiantian Chen ◽  
Yang Yang ◽  
Liyu Xie ◽  
Haijian Yang ◽  
Guangbin Dong ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dual Role ◽  
Allylic Alkylation ◽  
Cross Coupling Reaction ◽  
Neutral Conditions

<p>We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H<sub>2</sub>O is proposed to play a “dual role” in activating both the ketone and the diene substrate.</p>

Oxidase Catalysis via an Aerobically Generated Dess-Martin Periodinane Analogue

2018 ◽  
Author(s):  
Asim Maity ◽  
Sung-Min Hyun ◽  
Alan Wortman ◽  
David Powers
Keyword(s):  
Chemical Synthesis ◽  
Aerobic Oxidation ◽  
Substrate Oxidation ◽  
Oxidation Catalysis ◽  
Hypervalent Iodine ◽  
Oxidation Reactions ◽  
Broad Array ◽  
Oxidation Chemistry ◽  
Reactive Oxidants

<p>Hypervalent iodine(V) reagents, such as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to access these reagents from O2 would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. Here, we couple aerobic oxidation of iodobenzenes with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. Further, the developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.</p>

Retrospective prioritization of multiple items during working memory storage

2019 ◽  
Author(s):  
Ashley DiPuma ◽  
Kelly Rivera ◽  
Edward Ester
Keyword(s):  
Working Memory ◽  
Memory Performance ◽  
Memory Item ◽  
Neutral Condition ◽  
Memory Storage ◽  
Single Item ◽  
Incorrect Item ◽  
Memory Precision ◽  
Neutral Conditions ◽  
Directing Attention

Working memory (WM) performance can be improved by an informative cue presented during storage. This effect, termed a retro-cue benefit, can be used to explore mechanisms of attentional prioritization in WM. Directing attention to a single item stored in memory is known to increase memory precision while decreasing the likelihood of incorrect item reports and random guesses, but it is unclear whether similar benefits manifest when participants direct attention to multiple items stored in memory. We tested this possibility by quantifying memory performance when participants were cued to prioritize one or two items stored in working memory. Consistent with prior work, cueing participants to prioritize a single memory item yielded higher recall precision, fewer swap errors, and fewer guesses relative to a neutral cue condition. Conversely, cueing participants to prioritize two memory items yielded fewer swap errors relative to a neutral condition, but no differences in recall precision or guess rates. Although swap rates were less likely during the cue-two vs. neutral conditions, planned comparisons revealed that when participants made swap errors during cue-two trials they were far more likely to confuse two prioritized stimuli than they were to confuse a prioritized stimulus vs. a non-prioritized stimulus. Our results suggest that it is possible to prioritize multiple items stored in memory, with the caveat that doing so may increase the probability of confusing prioritized items.

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