Molecular Orbital Treatment of Activation Induced by Electron Attachment. Application to Electron Transfer Catalysis

1989 ◽  
pp. 225-243
Author(s):  
Keith F. Purcell ◽  
Michel Rajzmann ◽  
Michel Chanon ◽  
Henri Chermette ◽  
Chérifa Mehadji
Keyword(s):  
Electron Transfer ◽  
Molecular Orbital ◽  
Electron Attachment

A semi-empirical molecular orbital scheme to study electron transfer in iron–sulphur proteins

2005 ◽  
Vol 33 (1) ◽  
pp. 20-21 ◽  
Author(s):  
M. Sundararajan ◽  
J.P. McNamara ◽  
M. Mohr ◽  
I.H. Hillier ◽  
H. Wang
Keyword(s):  
Electron Transfer ◽  
Electronic Structure ◽  
Molecular Orbital ◽  
Parametric Method ◽  
Orbital Method ◽  
Molecular Orbital Method ◽  
Semi Empirical

We describe the use of the semi-empirical molecular orbital method PM3 (parametric method 3) to study the electronic structure of iron–sulphur proteins. We first develop appropriate parameters to describe models of the redox site of rubredoxins, followed by some preliminary calculations of multinuclear iron systems of relevance to hydrogenases.

Paramagnetic organometallic molecules. XIV. Ion-pair and steric effects in dissociative electron transfer reactions of metal cluster carbonyl radical anions

1983 ◽  
Vol 36 (3) ◽  
pp. 441 ◽  
Author(s):  
CM Kirk ◽  
BM Peake ◽  
BH Robinson ◽  
J Simpson
Keyword(s):  
Electron Transfer ◽  
Metal Cluster ◽  
Metal Carbonyl ◽  
Electron Attachment ◽  
Transfer Reactions ◽  
Organic Radical ◽  
Radical Anions ◽  
Dissociative Electron Attachment ◽  
Dissociative Electron Transfer ◽  
Electron Transfer Reactions

An investigation of electron attachment reactions of cluster metal carbonyls is presented. In general, alkyl and organometallic halides react rapidly with metal carbonyl cluster radical anions at ambient temperatures to give the neutral cluster molecule. Halide ion and alkyl or organometallic radicals are also produced, which indicate that these are dissociative electron attachment reactions analogous to those of organic radical anions. The rate of dissociative electron attachment in reactions of PhCCo3(CO)9- was found to depend on the R-X bond energy, the size of the alkyl group and the nature of the counter-ion. In particular, (Ph3P)2N+ retarded some electron transfer reactions to the extent that the bimolecular decay of PhCCo3(CO)9- effectively competed with the electron transfer process in determining the reaction path.

The Electroreduction of Substituted Benzofurazans

1972 ◽  
Vol 50 (2) ◽  
pp. 263-269 ◽  
Author(s):  
W. R. Fawcett ◽  
P. A. Forte ◽  
R. O. Loutfy ◽  
J. M. Prokipcak
Keyword(s):  
Electron Transfer ◽  
Molecular Orbital ◽  
Double Layer ◽  
Rate Constants ◽  
Hyperfine Splitting ◽  
Platinum Electrode ◽  
Hückel Theory ◽  
Layer Effect ◽  
Standard Rate ◽  
Anion Radicals

The electroreduction of 4- and 5-substituted benzofurazans was investigated at a platinum electrode in acetonitrile. Standard potentials for the reactions were linearly related to the energy of the lowest vacant molecular orbital as estimated by Hückel theory. Standard rate constants for electron transfer decreased as standard potentials in the series became more cathodic. This decrease is attributed to a double layer effect. No correlation was obtained between standard rate constants and observed hyperfine splitting constants for the anion radicals.

The oxidation of sulfides by chromium(V)

2003 ◽  
Vol 81 (1) ◽  
pp. 75-80 ◽  
Author(s):  
Carmela R Jackson Lepage ◽  
Lynn Mihichuk ◽  
Donald G Lee
Keyword(s):  
Electron Transfer ◽  
Molecular Orbital ◽  
Radical Cation ◽  
Oxygen Transfer ◽  
Single Electron ◽  
Frontier Molecular Orbital ◽  
Molecular Orbital Calculations ◽  
Single Electron Transfer ◽  
Oxidation Of Sulfides

The mechanism for the oxidation of sulfides by [(me4-salen)CrV(O)(pyO)]CF3SO3, where me4-salen is 8,8,8',8'-tetramethylsalen and pyO is pyridine N-oxide, has been investigated. Results from Hammett correlations on the rates of oxidation of substituted thioanisoles, frontier molecular orbital calculations, and product studies are consistent with a mechanism that is initiated by a single electron transfer to give a radical cation intermediate.Key words: oxidation, chromium(V), sulfides, radical cation, oxygen transfer.

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