CONTENTS LIST OF CONTRIBUTORS. ix PREFACE. . xi I. II. III. IV. V. VI. VII. VIII. IX. X. XI. XII. XIII. XIV. I. II. III. IV. Molecular Mechanics for Transition Metal Centers: From Coordination Complexes to Metalloproteins ROBERT J. DEETH Introduction . . . . . . . . . . . . . . . 1 Conventional Molecular Mechanics. . . . . . . . 2 Shortcomings of MM for TM Systems: Angular Potentials 4 Effects from d Electrons . . . . 5 Ligand Field Molecular Mechanics. . . . . . 8 LFMM Parameterization . . . . . . . . . 10 Simple Metal, Simple Ligand: Ga(III) Hydroxamates 11 Simple Metal, Complex Ligand: Mn(II) Carboxylates . 13 Difficult Metals: Jahn-Teller Effects in Cu(II) and the trans Influence in Pt(II) . . . . . . . . . . . . . 16 Spin States . . . . . . . . . . . . . . . 20 Metalloproteins and Molecular Dynamics: Copper Proteins 22 Bond Energies and Reaction Mechanisms: Water Exchange 28 Effects of M-L 1t Bonding. 33 Conclusions 36 Summary . 37 References. 37 Calculation of Magnetic Circular Dichroism Spectra With Time-Dependent Density Functional Theory MICHAEL SETH and TOM ZIEGLER Introduction 41 Theory. . 47 Applications 74 Concluding Remarks 100 List of Symbols . 101 Acknowledgments 103 References. 104 v
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CONTENTS
LIST OF CONTRIBUTORS. ix PREFACE. . xi
I. II.
III. IV. V.
VI. VII.
VIII. IX.
X. XI.
XII. XIII. XIV.
I. II.
III. IV.
Molecular Mechanics for Transition Metal Centers: From Coordination Complexes to Metalloproteins
ROBERT J. DEETH
Introduction . . . . . . . . . . . . . . . 1 Conventional Molecular Mechanics. . . . . . . . 2 Shortcomings of MM for TM Systems: Angular Potentials 4 Effects from d Electrons . . . . 5 Ligand Field Molecular Mechanics. . . . . . 8 LFMM Parameterization . . . . . . . . . 10 Simple Metal, Simple Ligand: Ga(III) Hydroxamates 11 Simple Metal, Complex Ligand: Mn(II) Carboxylates . 13 Difficult Metals: Jahn-Teller Effects in Cu(II) and the trans Influence in Pt(II) . . . . . . . . . . . . . 16 Spin States . . . . . . . . . . . . . . . 20 Metalloproteins and Molecular Dynamics: Copper Proteins 22 Bond Energies and Reaction Mechanisms: Water Exchange 28 Effects of M-L 1t Bonding. 33 Conclusions 36 Summary . 37 References. 37
Calculation of Magnetic Circular Dichroism Spectra With Time-Dependent Density Functional Theory
MICHAEL SETH and TOM ZIEGLER
Introduction 41 Theory. . 47 Applications 74 Concluding Remarks 100 List of Symbols . 101 Acknowledgments 103 References. 104
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Theoretical Investigation of Solvent Effects and.Complex Systems: Toward the calculations of bioinorganic systems from ab initio molecular dynamics
simulations and static quantum chemistry
MARC BRUSSEL, STEFAN ZAHN, E. HEy-HAWKINS and BARBARA KIRCHNER
I. Introduction . . . . . . . . . II. AIMD Simulations. . . . . . .
III. Static Quantum Chemical Calculations. IV. Conclusion
Acknowledgment References.
Simulations of Liquids and Solutions Based on Quantum Mechanical Forces
THOMAS S. HOFER, BERND M. RODE, ANDREAS B. PRIBIL
and BERNHARD R. RANDOLF
I. Introduction . . . . . . . . . . . II. Methodology of the QMCF Approach. . .
III. Applications of the QMCF MD Methodology IV. Conclusions . .
III. The Cluster Model Approach to Quantum Chemical Studies of Enzyme Reactions . . . . . . . .
IV. DFT Investigations of the AAH Mechanism. V. Conclusions . .
Acknowledgment References.
INDEX
CONTENTS OF PREVIOUS VOLUMES
437 449
452 456 491 495 495
501 515
LIST 0
William Ames Institut fOr Physikalische und Theol Chemie, Universitiit Bonn, Bonn, G
Marc Brussel Wilhelm-Ostwald Institut fOr Physik und Theoretische Chemie, Univers Leipzig, Leipzig, Germany
Gemma Christian Institut fOr Physikalische und Theoretische Chemie, Universitiit E Bonn, Germany
Aleix Comas-Vives Departament de Quimica, Universil Autonoma de Barcelona, Bellaterra Catalonia, Spain
Robert J. Deeth Department of Chemistry, Inorganic Computational Chemistry Group, U of Warwick, Coventry, United King£
E. Hey-HaWkins Institut fOr Anorganische Chemie, U Leip:?ig, Leipzig, Germany
Thomas S. Hofer Theoretical Chemistry Division, InSI of General, Inorganic and Theoretic Chemistry, University of Innsbruck, Innsbruck, Austria
Vidar R. Jensen Department of Chemistry, Universil of Bergen, Bergen, Norway
Mario Kampa Institut fOr Physikalische und Theoretische Chemie, Universitiit E Bonn, Germany
Barbara Kirchner Wilhelm-Ostwald Insfitut fOr Physik, und Theoretische Chemie, Univers, Leipzig, Leipzig, Germany
to
CONTENTS
LIST OF CONTRIBUTORS IX
PREFACE. . . . • xi
Luminescent Lanthanide Sensors
MORGAN L. CABLE, DANA J. LEVINE, JAMES P. KIRBY, HARRy B. GRAY
and ADRIAN PONCE
I. Introduction 2 II. Effects of Ancillary Ligands 10
III. Additional Factors That Govern Complex Stability . 30 IV. Looking to the Future 35 V. Conclusions 38
Acknowledgments 40 References 40
Photophysics of Soft and Hard Molecular Assemblies Based on Luminescent Complexes
CRISTIAN A. STRASSERT, MATTEO MAURO and LUISA DE COLA
I. Introduction 48 II. Basic Photophysics of Selected Transition Metal Complexes 50
III. Molecular Systems Based on Aggregates of d6 Metal Complexes . 54 IV. Molecular Systems Based on Aggregates of dB Metal Complexes . 73 V. Conclusions and Open Questions 93
References 94
Photochemistry and Photophysics of Metal Complexes with Dendritic Ligands
VINCENZO BALZANI, GIACOMO BERGAMINI and PAOLA CERONI
I. Dendrimers: A New Class of Ligands 106 II. Intrinsic Photochemical and Photophysical Properties of
Organic Dendrimers 108
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vi CONTENTS
III. Dendrimers with One or More Metal Complexes as . Branching Centers . . . . . . . . . . . .
IV. Coordination of Metal Ions Inside Dendrimers . . V. Coordination of Dendrimers Around Metal Ions .
Introduction. . . . . . Environmental Matter Unde Effect of Complexation and I Individual Compartments an Transition Metal Photochem: Atmospheric Gases. . .
V. Photooxidation of Organic Pc Complexes in Hydrosphere a
VI. Concluding Remarks Acknowledgments References . . . .
Photochemical Activation and by CT Excitation of F
ARND VOGLEF
I. Introduction. . . . . . II. Water Splitting . . . . .
III. Carbon Dioxide Splitting . IV. Dinitrogen Splitting . . V. Conclusion. . .
VI. Abbreviations . . Acknowledgment . References . . .
Visible Light Photocatalysis b Titania as a ~
I. Introduction. . . . . . II. Titania-Chloroplatinum(IV) l
III. Titania-Halogenorhodium(IIl IV. Summary and Outlook . .
Acknowledgments References. . . . . . .
vii
13 17 24 32 33
38 39 46 67 81 82
y
I ~88 i90
!~98 12 21 28
229
f29
: I
I
~36 ~37
~60 ~76 Z80 282 B82
CONTENTS
Transition Metal Complexes as Solar Photocatalysts in the Environment: A Short Review of Recent Development
Photocatalysis by Inorganic Solid Materials: Revisiting its Definition, Concepts, and Experimental Procedures
LIST 0B.OHTANI
I. Introduction . . . . . . II. Photocatalysis .
III. Principle of Photocatalysis . IV. Kinetics . . . . . . . . . . . V. Visible Light-Induced Photocatalysis
VI. Design of Active Photocatalysts VII. Concluding Remarks .
Acknowledgments References
INDEX. . • .
CONTENTS OF PREVIOUS VOLUMES
396 Luis G. Arnaut 397 Chemistry Department, University G
399 Cmmbm, Cmmbm, Portugm
406 414 Vincenzo Balzani
Dipartimento di Chimica "G. Ciamic421 Universita di Bologna, via Selmi 2,
425 Bologna, Italy 425 425 Giacomo Bergamini
Dipartimento di Chimica "G. Ciamic 431 Universita di Bologna, via Selmi 2, j
Italy441
Morgan L. Cable Planetary Science Section, Jet Prol Laboratory, and Beckman Institute, California Institute of Technology, Pasadena, CaMornm, USA
Paola Ceroni Dipartimento di Chimica "G. Ciamie Universita di Bologna, via Selmi 2, f Italy
Luisa De Cola Physikalisches Institut, WestfaJische Wi/hems Universitiit MOnster, Mendesltrasse 7, and Center for Nanotechnology, CeNTech, Heisenbergstrasse 11, MOnster, Gs,
Harry B. Gray Beckman Institute, California Institut Technology, Pasadena, Califomia, (
Hiroki Inumaru Department of Chemistry, Tokyo Ins Technology, Tokyo, Japan
Osamu Ishitani Core Research for Evolutional Seier Technology (CREST), Japan Scienc Technology Agency (JST), Kawagul Saftama, DepartmentofChemmt~,
Institute of Technology, Tokyo, and
.-
CONTENTS
LIST OF CONTRIBUTORS IX
PREFACE. . . . . xi
Predictive Studies of Oxygen Atom Transfer Reactions by Compound I of Cytochrome P450: Aliphatic and Aromatic Hydroxylation,
Epoxidation, and Sulfoxidation
SAM P. DE VISSER
I. Background. . . . . . . . . . . . . . . . . 2 II. Computational Studies of the Catalytic Activity of Heme
and Nonheme Enzymes . . . . . . . . . . 7 III. Trends in Substrate Oxidation Reactions 15 IV. Outlook and Conclusions 27
References . . 27
Heme-Containing Dioxygenases
IGOR EFIMOV, JASWIR BASRAN, SARAH J. THACKRAY, SANDEEP HANDA,
CHRISTOPHER G. MOWAT and EMMA LLOYD RAVEN
I. Introduction. . . . . . . . 34 II. Physiological Function . . . . 34
III. Heme Coordination Environment 35 IV. Steady-State Activity. . . 36 V. Expression Systems . . . . . . 37
III. Substitution of Ru(III)-pac Complexes . 185 IV. Reactions of RuIII-pac Complexes with DNA Constituents 188 V. Reactions of RuIII-pac Complexes with Sulfur-Containing
The Chemistry of Monovalent Copper in Aqueous Solutions
ARIELA BURG and DAN MEYERSTEIN
I. Introduction. . . . . . 220 II. Cu(l) in Aqueous Solutions . 220
III. Cu(l)Ln as a Reducing Agent 230 IV. Catalysis . . . . . . . . . . . 248 V. Summary. 255
References . . . . . . . . . . 256
Hypothiocyanite
MICHAEL T. AsHBY
I. Introduction. . . . . . . . . . . 264 II. Molecular Structure, Properties, and Synthesis . 266
III. Reaction Mechanisms . . . . . . . . . . 275
-
.
viii CONTENTS
IV. V.
Biological Relevance . Conclusions and Outlook Acknowledgments References . . . . . .
292 298 299 299 LIST a
INDEX. . . . . . . . • .
CONTENTS OF PREVIOUS VOLUMES .
305 317
Michael T. Ashby Department of Chemistry and Bioe University of Oklahoma, Norman, C USA
Jaswir Basran Department of Biochemistry, Henf] WeI/come Building, University of L Leicester, United Kingdom
Damian E. Bikiel Departamento de Quimica Inorgan Analftica y Quimica Ffsica/lNQUlM CONICET, Buenos Aires, Argentini
Ariane Brausam Department of Chemistry and Phal Unfversity of Erlangen-NOrnberg, Eger/andstr. 1, Erlangen, Germany
Ariela Burg Chemical Engfneering Departmen~
Shamoon Col/ege of Engineering, Sheva, Israel
Debabrata Chatterjee Chemistry and Biomimetics Group, Central Mechanical Engineering R< Institute, Durgapur, India
Sam P. de Visser The Manchester Interdisciplinary E and the School of Chemfcal Enginl and Analytical Science, University Manchester, Manchester, United ~
Fabio Doctorovich Departamento de Qufmica Inorgan Analftica y Qufmica Ffsica/lNQUIM CONICET, Buenos Aires, Argentim
Igor Efimov Department of Chemistry, Universh Leicester, Leicester, United Kingd(
Milos R. Filipovic Department of Chemistry and Phal University of Erlangen-NOrnberg, Egerlandstrasse 1, Erlangen, Gem