scholarly journals Why Intermolecular Nitric Oxide (NO) Transfer? Exploring the Factors and Mechanistic Aspects of NO Transfer Reaction

2022 ◽  
Author(s):  
Sandip Das ◽  
Kulbir kulbir ◽  
Soumyadip Ray ◽  
Tarali Devi ◽  
Somnath Ghosh ◽  
...  

Small molecule activation & their transfer reactions in biological or catalytic reactions are greatly influenced by the metal-centers and the ligand frameworks. Here, we report the metal-directed nitric oxide (NO)...

Author(s):  
Peter Werner Roesky ◽  
Niklas Reinfandt ◽  
Nadine Michenfelder ◽  
Christoph Schoo ◽  
Ravi Yadav ◽  
...  

Author(s):  
Leila G. Ranis ◽  
Jacqueline Gianino ◽  
Justin M. Hoffman ◽  
Seth N. Brown

Eight-coordinate MoO2(DOPOQ)2 can donate two oxygen atoms to substrates such as phosphines in a four-electron nonclassical oxygen atom transfer reaction.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
P. Krishnaveni ◽  
V. Ganesh

AbstractModern day hospital treatments aim at developing electrochemical biosensors for early diagnosis of diseases using unconventional human bio-fluids like sweat and saliva by monitoring the electron transfer reactions of target analytes. Such kinds of health care diagnostics primarily avoid the usage of human blood and urine samples. In this context, here we have investigated the electron transfer reaction of a well-known and commonly used redox probe namely, potassium ferro/ferri cyanide by employing artificially simulated bio-mimics of human sweat and saliva as unconventional electrolytes. Typically, electron transfer characteristics of the redox couple, [Fe(CN)6]3−/4− are investigated using electrochemical techniques like cyclic voltammetry and electrochemical impedance spectroscopy. Many different kinetic parameters are determined and compared with the conventional system. In addition, such electron transfer reactions have also been studied using a lyotropic liquid crystalline phase comprising of Triton X-100 and water in which the aqueous phase is replaced with either human sweat or saliva bio-mimics. From these studies, we find out the electron transfer reaction of [Fe(CN)6]3−/4− redox couple is completely diffusion controlled on both Au and Pt disc shaped electrodes in presence of sweat and saliva bio-mimic solutions. Moreover, the reaction is partially blocked by the presence of lyotropic liquid crystalline phase consisting of sweat and saliva bio-mimics indicating the predominant charge transfer controlled process for the redox probe. However, the rate constant values associated with the electron transfer reaction are drastically reduced in presence of liquid crystalline phase. These studies are essentially carried out to assess the effect of sweat and saliva on the electrochemistry of Fe2+/3+ redox couple.


2021 ◽  
Author(s):  
Qiuran Wang ◽  
Sam H. Brooks ◽  
Tianchang Liu ◽  
Neil C. Tomson

This Feature Article describes recent advances in the design of multinucleating ligands that support small molecule activation chemistry.


2016 ◽  
Vol 12 ◽  
pp. 1372-1379 ◽  
Author(s):  
Stefan Mark ◽  
Hubert Wadepohl ◽  
Markus Enders

A series of Cr(III) complexes based on quinoline-cyclopentadienyl ligands with additional hemilabile side arms were prepared and used as single-site catalyst precursors for ethylene polymerization. The additional donor functions interact with the metal centers only after activation with the co-catalyst. Evidence for this comes from DFT-calculations and from the differing behavior of the complexes in ethylene polymerization. All complexes investigated show very high catalytic activity and the additional side arm minimizes chain-transfer reactions, leading to increase of molecular weights of the resulting polymers.


2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.


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