Site selectivity studies on heterobimetallic complexes: substitution reactions of (.eta.5-C5H5)MM'(CO)8 (M = Mo, W; M' = Mn, Re)

1992 ◽  
Vol 31 (20) ◽  
pp. 4084-4090 ◽  
Author(s):  
Wayne L. Ingham ◽  
Neil J. Coville
Keyword(s):  
Substitution Reactions ◽  
Heterobimetallic Complexes ◽  
Site Selectivity ◽  
Selectivity Studies

Cycloheptatrienyl-bridged heterobimetallic complexes: facile phosphine substitution reactions of [cyclic] (.mu.-C7H7)Fe(CO)3Rh(CO)2

1986 ◽  
Vol 5 (5) ◽  
pp. 829-839 ◽  
Author(s):  
Richard G. Ball ◽  
Frank. Edelmann ◽  
Gong Yu. Kiel ◽  
Josef. Takats ◽  
Ronald. Drews
Keyword(s):  
Substitution Reactions ◽  
Heterobimetallic Complexes

scholarly journals Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine, Perfluoropyridazine, and Perfluoropyrazine

Molecules ◽  
2021 ◽  
Vol 26 (24) ◽  
pp. 7637
Author(s):  
Timothy J. Fuhrer ◽  
Matthew Houck ◽  
Rachel M. Chapman ◽  
Scott T. Iacono
Keyword(s):  
High Performance ◽  
Density Functional ◽  
Substitution Reactions ◽  
Regioselective Substitution ◽  
Site Selectivity ◽  
Π Complex ◽  
Synthetic Scaffolds ◽  
Polyaryl Ethers ◽  
A Site ◽  
Drug Scaffolds

Perfluoroaromatics, such as perfluoropyridine and perfluorobenzene, are privileged synthetic scaffolds in organofluorine methodology, undergoing a series of regioselective substitution reactions with a variety of nucleophiles. This unique chemical behavior allows for the synthesis of many perfluoroaromatic derived molecules with unique and diverse architectures. Recently, it has been demonstrated that perfluoropyridine and perfluorobenzene can be utilized as precursors for a variety of materials, ranging from high performance polyaryl ethers to promising drug scaffolds. In this work, using density functional theory, we investigate the possibility of perfluoropyrimidine, perfluoropyridazine, and perfluoropyrazine participating in similar substitution reactions. We have found that the first nucleophilic addition of a phenoxide group substitution on perfluoropyrimidine and on perfluoropyridazine would happen at a site para to one of the nitrogen atoms. While previous literature points to mesomeric effects as the primary cause of this phenomenon, our work demonstrates that this effect is enhanced by the fact that the transition states for these reactions result in bond angles that allow the phenoxide to π-complex with the electron-deficient diazine ring. The second substitution on perfluoropyrimidine and on perfluoropyridazine is most likely to happen at the site para to the other nitrogen. The second substitution on perfluoropyrazine is most likely to happen at the site para to the first substitution. The activation energies for these reactions are in line with those reported for perfluoropyridine and suggest that these platforms may also be worth investigation in the lab as possible monomers for high performance polymers.

scholarly journals Infrared multiphoton excitation of deuterated dodecanes: final product and photolonization mass spectroscopic site selectivity studies

1984 ◽  
Author(s):  
C. E. Geosling ◽  
T. J. Manuccia ◽  
J. Laukamper ◽  
A. MacRobert ◽  
D. Feldmann ◽  
...  
Keyword(s):  
Multiphoton Excitation ◽  
Site Selectivity ◽  
Selectivity Studies
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