scholarly journals The Substituent Effect on the Energy Profiles of Inter and Intramolecular Proton Transfers between Phosphine Oxide-Phosphinous Acid Tautomers

2016 ◽  
Vol 27 (4) ◽  
pp. 210-220 ◽  
Author(s):  
Hossein Tavakol ◽  
Fariba Keshavarzipour
Keyword(s):  
Phosphine Oxide ◽  
Substituent Effect ◽  
Phosphinous Acid ◽  
Energy Profiles ◽  
Proton Transfers

Regium bonds formed by MX (M═Cu, Ag, Au; X═F, Cl, Br) with phosphine-oxide/phosphinous acid: comparisons between oxygen-shared and phosphine-shared complexes

2019 ◽  
Vol 117 (18) ◽  
pp. 2443-2455 ◽  
Author(s):  
Baishu Zheng ◽  
Yi Liu ◽  
Zhaoxu Wang ◽  
Fengxiang Zhou ◽  
Yuan Liu ◽  
...  
Keyword(s):  
Phosphine Oxide ◽  
Phosphinous Acid

Electronic aspects of the phosphine-oxide → phosphinous acid tautomerism and the assisting role of transition metal centers

2014 ◽  
Vol 760 ◽  
pp. 177-185 ◽  
Author(s):  
Gabriele Manca ◽  
Maria Caporali ◽  
Andrea Ienco ◽  
Maurizio Peruzzini ◽  
Carlo Mealli
Keyword(s):  
Transition Metal ◽  
Phosphine Oxide ◽  
Phosphinous Acid ◽  
Metal Centers

Three- versus four-coordinate phosphorus in the gas phase and in solution: Treacherous relative energies for phosphine oxide and phosphinous acid

2002 ◽  
Vol 116 (1) ◽  
pp. 112 ◽  
Author(s):  
Steven S. Wesolowski ◽  
Nicole R. Brinkmann ◽  
Edward F. Valeev ◽  
Henry F. Schaefer ◽  
Matthew P. Repasky ◽  
...  
Keyword(s):  
Gas Phase ◽  
Phosphine Oxide ◽  
Phosphinous Acid

Intramolecular Proton Transfer in the Isomerization of Hydroxyacetone: A Detailed Characterization Based on Reaction Force Analysis and the Bond Fragility Spectrum

2020 ◽  
Author(s):  
Wallace Derricotte ◽  
Huiet Joseph
Keyword(s):  
Chemical Potential ◽  
Reaction Force ◽  
Intramolecular Proton Transfer ◽  
Intermediate Energy ◽  
Force Analysis ◽  
Activation Energy Barrier ◽  
Detailed Characterization ◽  
Proton Transfers ◽  
Reaction Force Constant

The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol<sup>-1</sup>. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.

Substituent effect on wave numbers of C=O valence vibrations in ferrocene derivatives

1983 ◽  
Vol 48 (6) ◽  
pp. 1635-1646 ◽  
Author(s):  
Alexander Perjéssy ◽  
Štefan Toma
Keyword(s):  
Linear Correlation ◽  
Substituent Effect ◽  
Empirical Relation ◽  
Ferrocene Derivatives ◽  
Wave Numbers ◽  
Complex Structural ◽  
Transmission Factors

Wave numbers of C=O valence vibrations of 83 ferrocene derivatives have been measured in tetrachloromethane. For a series of 154 compounds containing ferrocene skeleton linear correlation has been found between wave numbers of C=O vibration and X+(R) constants of structural fragments in the sense of modified and extended Seth-Paul-Van Duyse equation. Validity has been verified of the recently derived empirical relation for calculation of the X+(R) constants of complex structural fragments from values of constants of substituents and transmission factors for simple structural groupings. The transmission factors γ and π' for 1,3- and 1,1'-ferrocene system have been found to be well applicable to calculation of constants of structural fragments containing ferrocene skeleton.

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