π* Molecular Orbital Crossing a2(χ)/b1(ψ) in 1,10-Phenanthroline Derivatives.Ab InitioCalculations and EPR/ENDOR Studies of the 4,7-Diaza-1,10-phenanthroline Radical Anion and Its M(CO)4Complexes (M = Cr, Mo, W)

1996 ◽  
Vol 35 (5) ◽  
pp. 1295-1300 ◽  
Author(s):  
Sylvia Ernst ◽  
Conny Vogler ◽  
Axel Klein ◽  
Wolfgang Kaim ◽  
Stanislav Zališ
Keyword(s):  
Molecular Orbital ◽  
Radical Anion ◽  
Orbital Crossing

Fragmentation Rates of Aromatic Radical Anions and the π*— σ* Orbital Crossing Point

1984 ◽  
Vol 39 (1) ◽  
pp. 49-54 ◽  
Author(s):  
H. O. Villar ◽  
E. A. Castro ◽  
R. A. Rossi
Keyword(s):  
Carbon Atom ◽  
Molecular Orbital ◽  
Qualitative Agreement ◽  
Radical Anion ◽  
Reaction Coordinate ◽  
Radical Anions ◽  
Aromatic Radical ◽  
Orbital Crossing ◽  
Crossing Point

The reaction coordinate of the fragmentation of aromatic radical anions with nucleofugal groups was studied by the INDO and MNDO techniques. The reaction coordinate turned out as the stretching between the nucleofugal group bonded to the carbon atom of the aryl moiety. It was found that to fragment a π* radical anion, the odd electron has to be transferred to the σ* molecular orbital of the aryl-nucleofugal bond by an orbital crossing, which is reached by the lengthening of this bond. There is a qualitative agreement between the length of the bond to reach the orbital crossing point and the experimental fragmentation rates of the aromatic radical anions. Finally, some considerations about the σ-π coupling are made, since it is defining the possibility of a transfer from the π* to the σ* molecular orbital.

Resonance Raman, electron spin resonance and molecular orbital studies of m-benzosemiquinone radical anion

1986 ◽  
Vol 90 (17) ◽  
pp. 3968-3975 ◽  
Author(s):  
G. N. R. Tripathi ◽  
D. M. Chipman ◽  
C. A. Miderski ◽  
H. Floyd Davis ◽  
Richard W. Fessenden ◽  
...  
Keyword(s):  
Electron Spin Resonance ◽  
Molecular Orbital ◽  
Electron Spin ◽  
Radical Anion ◽  
Resonance Raman ◽  
Spin Resonance

Reactions of a distonic peroxyl radical anion influenced by SOMO–HOMO conversion: an example of anion-directed channel switching

2020 ◽  
Vol 22 (4) ◽  
pp. 2130-2141
Author(s):  
Sui So ◽  
Benjamin B. Kirk ◽  
Uta Wille ◽  
Adam J. Trevitt ◽  
Stephen J. Blanksby ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Radical Anion ◽  
Peroxyl Radical ◽  
Remote Site ◽  
Channel Switching ◽  
Anion Site

Deprotonation of a remote site in a peroxyl radical energetically buries the singly occupied molecular orbital, suppressing radical-driven oxidation and promoting reactions involving the anion site.

Resonance Raman and molecular orbital studies of the effects of deuteration on the vibrational structure of the p-benzosemiquinone radical anion

1983 ◽  
Vol 87 (26) ◽  
pp. 5357-5361 ◽  
Author(s):  
Robert H. Schuler ◽  
G. N. R. Tripathi ◽  
Michael F. Prebenda ◽  
Daniel M. Chipman
Keyword(s):  
Molecular Orbital ◽  
Radical Anion ◽  
Resonance Raman ◽  
Vibrational Structure

The Electron Spectra of a Blue S-Tetrazine Derived Betaine and its Protonated Forms A Comparison with the Radical Anion 1,5-Dimethyl-5-oxoverdazyl-3-olate

1984 ◽  
Vol 39 (12) ◽  
pp. 1790-1794 ◽  
Author(s):  
Helmut Vogler ◽  
Franz A . Neugebauer
Keyword(s):  
Molecular Orbital ◽  
Radical Anion ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Electron Spectra ◽  
Protonated Forms ◽  
Wavelength Absorption

The striking similarities of the hypsochromic shifts of the longest wavelength absorption observed in the serie 1-3 and 4 -6 are rationalized by means of simple molecular orbital theory.

Sulfonyl esters. 2. CS cleavage in some substitution reactions of nitrobenzenesulfonates

1990 ◽  
Vol 68 (8) ◽  
pp. 1450-1455 ◽  
Author(s):  
James Clayton Baum ◽  
Jimat Bolhassan ◽  
Richard Francis Langler ◽  
Paul Joseph Pujol ◽  
Raj Kumar Raheja
Keyword(s):  
Electron Transfer ◽  
Molecular Orbital ◽  
Radical Anion ◽  
Nucleophilic Aromatic Substitution ◽  
Bond Rupture ◽  
Single Electron Transfer ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Nucleophilic Aromatic Substitutions ◽  
Aromatic Sulfonate

An attempt to explore aromatic sulfonate esters as agents for the condensation of alcohols with mercaptans revealed an unusual process for sulfonate esters: CS bond rupture. Two mechanistic possibilities for CS bond rupture are explored: (i) radical anion intermediacy via single electron transfer and (ii) nucleophilic aromatic substitution. Both experiments and molecular orbital computations are presented to support the conclusion that nucleophilic aromatic substitutions are occurring. Keywords: sulfonyl esters, nitrobenzenesulfonates, CS bond rupture.

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