Electron Transfer II

198 Pages·1996·3.487 MB·English

by  Timothy Clark (auth.), J. Mattay (eds.)

77
Topics in Current Chemistry
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Electron Transfer II
: r o t i d E y .aJt t a M
With contributions by
R. Bassi, T. Clark, A. Heidbreder,
S. Hintz, R. C. Jennings, J. M. Kelly,
A. Kirsch-De Mesmaeker, J.-P. Lecomte,
J. Mattay, S. Steenken, G. Zucchelli
htiW 91 ,serugiF 4 selbaT dna 111 semehcS
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Preface
Like the 1994-issue of the series "Electron Transfer", the second volume again
covers various aspects of this fundamental process. The articles are concerned with
the experimental and theoretical aspects of electron transfer in chemisatnrdy biology.
In the latter, emphasis is given to energy transfer, which is alpsaor t of photosynthesis.
The concept of electron-transfer catalysis by metal ions is thoroughly discussed
in the first chapter on the basis of ab initio calculations, indicating its importance
for a variety of fundamental organic reactions. The second article is concerned with
transition metals such as Ru(II), Rh(IIl) and Co(Ill) which bind to DNA. Upon
photolysis, electron transfer processes are initiated, leading in general to damage of
the DNA molecule. Theu se of metalc omplexes as probes for studying the structure
of nucleic acids and potential photo-therapeutic applications are discussed. The
third chapter is devoted to cyclization reactions of radical ions, independent of
their generation by chemical, electrochemical or photochemical methods. The scope
of this new synthetic method has by far not reached its limitations and future
ivestigatiownisl l prove its potential compared to the radical and ionic counterparts.
The role of electron transfer in redox reations between radicals and organic molecules
is discussed in the fourth articleI.n general, electron transfer occurs after heterolysis
of an "addition product" (inner sphere). Addition takes place even in these cases
electron transfer is strongly exothermic. These findings indicate that inner-sphere
electron transfer processes are of more fundamental importance than the outher-
sphere reactions of organic chemistry. The final chapter is less concerned with
electron transfer than with energy transfer processes. However, the light-harvesting
antenna systems of higher plants are as important as the reaction centres themselves,
where charge separation takes place. Without these photosystems the world would
not exist, at least in its familiar form.
As stated earlier, the presentr eviews again refletchte interdisciplinary character
of electron-transfer research. I am very grateful to the authors for their efforts and
in some cases for their patience during the period from submission to printing. The
support given while preparing this volume by Dr. Hertel, Dr. Stumpe and their
team at the Springer-Verlag is also gratefully acknowledged.
Mtinster, September 1995 Jochen Mattay
Table of Contents
Ab Initio Calculations on Electron-Transfer
Catalysis by Metal Ions
T. Clark ..........................................
Photoreactions of Metal Complexes with DNA,
Especially Those Involving a Primary Photo-Electron
Transfer
A. Kirsch-De Mesmaeker, J.-P. Lecomte, J. M. Kelly ........ 25
Radical Ion Cyclizations
S. Hintz, A. Heidbreder, J. Mattay ...................... 77
One Electron Redox Reactions between Radicals
and Organic Molecules. An Addition/Elimination
(Inner-Sphere) Path
S. Steenken ....................................... 125
Antenna Structure and Energy Transfer in
Higher Plant Photosystems
R. C. Jennings, G. Zucchelli, R. Bassi .................. 147
Author Index Volumes 151 - 177 ...................... 381
Table of Contents of Volume 169
Electron Transfer I
Radical Ions: Where Organic Chemistry Meets Materials
Sciences
M. Baumgarten, K. Mtillen
Photoinduced Charge Transfer Processes at Semiconductor
Electrodes and Particles
R. Memming
Umpolung of Ketones via Enol Radical Cations
M. Schmittel
Thermal and Light Induced Electron Transfer Reactions
of Main Group Metal Hybrides and Organometallics
W. Kaim
Photoinduced Charge Separation via Twisted Intramolecular
Charge Transfer States
W. Rettig
Addition and Cycloaddition Reactions via Photoinduced
Electron Transfer
K. Mizuno, .Y Otsuji
Photophysical and Photochemical Properties of Fuilerenes
C. .S Foote
Ab lnitio Calculations on Electron-Transfer Catalysis
by Metal Ions
Timothy Clark
Computer-Chemie-Centrums des Instituts ffir Organische Chemic der Friederich-Alexander-
t~tisrevinU Edangen-N~rnberg, eBartshcabstegi/N ,52 Germany Erlangen, D-91052
Table of Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . 2
2 "Hole-Catalyzed" Reactions . . . . . . . . . . . . . . . 3
3 Calculational Methods for Radicals, Radical Ions and Radical
Reactions . . . . . . . . . . . . . . . . . . . . . . 8
4 Radical Ion Reaction Mechanisms . . . . . . . . . . . . . 11
4.1 Cycloadditions . . . . . . . . . . . . . . . . . . 11
4.2 Sigmatropic Rearrangements . . . . . . . . . . . . . 13
4.3 Electrocyclic Reactions . . . . . . . . . . . . . . . 14
5 Electron-Transfer from Metal Ions . . . . . . . . . . . . 15
6 Electron-Transfer Catalyzed Reactions . . . . . . . . . . . 16
6.1 1,3-Hydrogen Shifts . . . . . . . . . . . . . . . . 16
6.2 Cyclopropane Ring-Opening . . . . . . . . . . . . . 17
6.3 Ethylene Dimerization . . . . . . . . . . . . . . . 19
6.4 C-C Bond Activation and Cycloalkane Ring-Opening by
Transition Metal Atoms . . . . . . . . . . . . . . 20
6.50xirane Ring-Opening . . . . . . . . . . . . . . . 20
7 Summary and Outlook . . . . . . . . . . . . . . . . . 22
8 References . . . . . . . . . . . . . . . . . . . . . 22
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