Stereochemistry and product distribution in the thiono-thiolo rearrangement of phosphorothioic esters. 4. Role of leaving-group solvation

1981 ◽  
Vol 46 (8) ◽  
pp. 1625-1630 ◽  
Author(s):  
K. Bruzik ◽  
W. J. Stec
Keyword(s):  
Product Distribution ◽  
Leaving Group

Unexpected formation and conversion: role of substituents of 1,3-ynones in the reactivity and product distribution during their reactions with Ru3(CO)12

2019 ◽  
Vol 43 (3) ◽  
pp. 1478-1486
Author(s):  
Lei Xu ◽  
Liping Jiang ◽  
Shasha Li ◽  
Guofang Zhang ◽  
Weiqiang Zhang ◽  
...  
Keyword(s):  
Product Distribution ◽  
Molecular Structures ◽  
Steric Effects ◽  
Unexpected Formation ◽  
Electronic And Steric Effects

Electronic and steric effects of the substituents in 1,3-ynones play key roles in the product distribution and molecular structures.

Empirical σ Molecular Orbital Parameters and their Correlation with Rates of Substitution Reactions in Quadrate Cr(III) and Co(III) Complexes

1971 ◽  
Vol 49 (9) ◽  
pp. 1497-1501 ◽  
Author(s):  
C. H. Langford
Keyword(s):  
Field Theories ◽  
Complete Analysis ◽  
Substitution Reactions ◽  
Spectral Parameters ◽  
Empirical Measures ◽  
Orbital Parameters ◽  
Spectral Bands ◽  
Leaving Group ◽  
The Relationship

Empirical measures of σ bonding involving metal 3d orbitals are derived from Perumareddi's (4) complete analysis of the quartet spectral bands of quadrate complexes in the families Cr(NH3)5Xn+ and Cr(OH2)5Xn+. These are shown to correlate with lability of X in the Cr(III) complexes and in Co(NH3)5Xn+ complexes in a sense indicating that relative reactivity is controlled by variation of ligand metal 3d σ interaction. The relationship between the two Cr(III) series implies that the non-labile ligands can labilize the leaving group in proportion to their σ donor capacities. This observation bears on some well-known difficulties in crystal field theories of reactivity. In evaluating the correlation of spectral parameters with reactivity, the role of solvation in reactivity of Cr(III) and Co(III) complexes is discussed with emphasis on the surprisingly small solvent effects that have been observed.

Strategies for Constructing Reaction Networks of Lubricant Degradation

2005 ◽  
Author(s):  
Jim Pfaendtner ◽  
Linda J. Broadbelt ◽  
Q. Jane Wang
Keyword(s):  
Predictive Power ◽  
Quantitative Description ◽  
Product Distribution ◽  
Reaction Networks ◽  
Individual Species ◽  
Mechanistic Models ◽  
Lubricant Degradation ◽  
Fundamental Understanding ◽  
Secondary Reactions

Automated mechanism generation is an essential tool to be able to create mechanistic models of lubricant degradation chemistry. To date, modeling of lubricant degradation has been accomplished only through the use of lumped or pathways-style approaches. These methods have yielded important insights into major degradation pathways but lack predictive power and fail to produce some key trends in the product distribution, even qualitatively. Mechanistic models of lubricant degradation include reactivity of individual species as well as the role of secondary reactions. Such models have much to offer in terms of fundamental understanding of degradation chemistry. Furthermore, they may be exploited to directly study the effect of radical stabilizers and additives. Key results obtained include a quantitative description of the degradation of a model lubricant as well as detailed kinetic correlations for estimating rate constants. This poster presents our efforts to construct detailed reaction mechanisms of lubricant degradation. The underlying theories of automated network generation and preliminary results are presented.

n-Hexadecane hydroisomerization over Pt/ZSM-12: role of Si/Al ratio on product distribution

2013 ◽  
Vol 20 (5) ◽  
pp. 1023-1029 ◽  
Author(s):  
Sunil Mehla ◽  
K. R. Krishnamurthy ◽  
B. Viswanathan ◽  
Mathew John ◽  
Yogesh Niwate ◽  
...  
Keyword(s):  
Product Distribution
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