333; e by g

ODS

use 'al

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

vi CONTENTS

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 . .

Acknowledgment References. . .

Spin Interactions in Cluster Chemistry

MAREN PODEWITZ and MARKUS REIHER

I. Introduction . . . . . . . . . . . II. Theoretical Foundations . . . . . . .

III. From Dirac-Breit to Breit-Pauli Hamiltonians IV. Phenomenological Spin Hamiltonians. : . V. Concept of Local Electronic Spins. . . .

VI. Technical Issues: Optimization of Broken-Symmetry Determinants. VII. Studies on Open-Shell Polynuclear Transition-Metal Clusters

VIII. Conclusions . . Acknowledgments References.

III 113 133 136 137 137

143 147 159 172

172 173

177 179 189 194 203 213 216 224 225 225

Inner- and Oute AC

ALEIX COMAS-VIVI

I. Introduction . . . . II. Reaction Mechanisms f(

The Substrate Viewpoin III. Computational Investiga IV. Concluding Remarks

Acknowledgements. References. . . .

Computational Studies

I. Introduction . . . . II. Models and Methods .

III. Geometries and Electron IV. Metalation of Porphyrin~

V. Binding of Small Molecl VI. Summary and Conclusio

Acknowledgements. References. . . . .

Dealing with Complexi1 from a Theoretical P

Spectros(

FRANK NEESE, WILLIAM AM

G. LIAKOS, DIMITRIO~

SURAW,

I. Introduction . . . . II. Calculation of Reaction I

III. EPR of Degenerate Syste IV. Metal-Radicallnteractio V. Magnetic Properties of 0

VI. Concluding Remarks References. . . . .

L

VII

233 240 255 257 257

231

261 264 266 269 279 292 293 293

301 303 313 324 333 344 345

Dealing with Complexity in Open-Shell Transition Metal Chemistry from a Theoretical Perspective: Reaction Pathways, Bonding,

Spectroscopy, and Magnetic Properties

TATYANA E. SHUBINA

I. Introduction . . . . . . . . . . . . . II. Reaction Mechanisms for Hydrogenation Reactions:

The Substrate Viewpoint. . . . . . . . . III. Computational Investigation of Hydrogenation Mechanisms. IV. Concluding Remarks

Acknowledgements. References. . . .

Inner- and Outer-Sphere Hydrogenation Mechanisms: A Computational Perspective

CONTENTS

ALEIX COMAS-VIVES, GREGORI UJAQUE and AGUSTi LLEOOS

Computational Studies on Properties, Formation, and Complexation of M(II)-Porphyrins

I. Introduction . . . . . . . . . . . . II. Models and Methods . . . . . . . . .

III. Geometries and Electronic States of Metalloporphyrins IV. Metalation of Porphyrins . V. Binding of Small Molecules

VI. Summary and Conclusions Acknowledgements. References. . . . . .

I. Introduction . . . . . . . II. Calculation of Reaction Pathways

III. EPR of Degenerate Systems. . IV. Metal-Radical Interactions . . V. Magnetic Properties of Oligonuclear Clusters

VI. Concluding Remarks References. . . . . . . . . . . .

FRANK NEESE, WILLIAM AMES, GEMMA CHRISTIAN, MARIO KAMPA, DIMITRIOS

G. LIAKOS, DIMITRIOS A. PANTAZIS, MICHAEL ROEMELT, PANIDA

SURAWATANAWONG and SHENGFAYE

143 147 159 172 172 173

III 113 133 136 137 137

177 179 189 194 203 213 216 224 225 225

IRCHNER

s: Toward rdynamics

viii CONTENTS

Vibronic Coupling in Inorganic Systems: Photochemistry, Conical Intersections, and the Jahn-Teller and

Pseudo-Jahn-Teller Effects

RUSSELL G. MCKINLAY, JUSTYNA M. ZUREK and MARTIN J. PATERSON

I. Introduction . . . . . . . . . . . . . . . . 351 II. Theoretical and Computational Background. . . . . . 354

III. Important Computational Results in Inorganic Photochemistry 362 IV. Case Studies. . . . . 365 V. Conclusions and Outlook. 386

Acknowledgments 386 References. . . . . . 386

Elementary Reactions in Polynuclear Ions and Aqueous-Mineral Interfaces: A New Geology

JAMES R. RUSTAD

I. Molecular Geology. . . . . . . . 391 II. Modeling Tools for Geochemical Systems 393

III. Example Systems . . . . . . . . 402 IV. Geological Problems with Molecular Level Solutions 428

References. . . . . . . . . . . . . . . 433

The Aromatic Amino Acid Hydroxylase Mechanism: A Perspective from Computational Chemistry

ELAINE OLSSON, KNUT TEIGEN, AURORA MARTINEZ and VIDAR R. JENSEN

I. Introduction . . . . . . . . . . . . . . . . II. Structural Information. . . . . . . . . . . . .

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

v

c I,

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 .

VI. Conclusion References . . . . . . . . . . . . . .

113 117 124 132 133

Photochemistry and Photocatalysis of Rhenium(l) Diimine Complexes

HIROYUKI TAKEDA, KAzumDE KOIKE, TATSUKI MORIMOTO,

HIROKI INuMARu and OSAMU IsmTANI

I. II.

III. IV.

Introduction. . . . . . . . . . . . . Photophysics of Rhenium(l) Diimine Complexes Photochemistry of Rhenium(l) Complexes . Rhenium(l) Complexes as Highly Efficient Photocatalyst Acknowledgments References . . . . . . . . . . . . . . . . .

138 139 146 167 181 182

Design of Porphyrin-Based Photosensitizers for Photodynamic Therapy

LUIS G. ARNAUT

I. II.

III. IV. V.

VI.

Introduction. . . . . . . . . Molecular and Electronic Structure . Electronic Transitions. . . . . . Photoinduced Reactions with Molecular Oxygen Photodynamic Therapy. . . . . . . . Conclusions. . . . . . . . . . . Acknowledgments References . . . . . . . . . . .

.

Photosensitization and Photocatalysis in Bioinorganic, Bio-Organometallic and Biomimetic Systems

GUNTHER KNbR and UWE MONKOWIUS

I. II.

III. IV. V.

Introduction. . . . . . . . . . . . Inorganic Photochemistry Inspired by Nature Design Strategies and Building Blocks . Selected Applications . Concluding Remarks Acknowledgments References . . . .

188 190 198 212 221 228 229 229

236 237 260 276 280 282 282

Transition Metal Complexes as A Short Reviev.

ZOI

I. II.

III.

IV.

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

ZOFIA STASICKA

I. Introduction. . . . . . . . . . . . . . . . .. 292 II. Environmental Matter Under Sunlight Impact . . . . .. 293

III. Effect of Complexation and Photochemistry on Composition of Individual Compartments and Transport Between Them 296

IV. Transition Metal Photochemistry in Conversion of Some Atmospheric Gases . . . . . . . . . . . . . . 299

V. Photooxidation of Organic Pollutants by Transition Metal Complexes in Hydrosphere and Soils 316

VI. Concluding Remarks 333 Acknowledgments 334 References . . . . 334

Photochemical Activation and Splitting of H20, CO2 , and N2 Induced

I. II.

III. IV. V.

VI.

by CT Excitation of Redoxactive Metal Complexes

ARND VOGLER and HORST KUNKELY

Introduction. . . . . . . 346 Water Splitting. . . . . . 347 Carbon Dioxide Splitting . 353 Dinitrogen Splitting . 360 Conclusion. . . 367 Abbreviations . . 367 Acknowledgment . 367 References . . . 367

Visible Light Photocatalysis by Metal Halide Complexes Containing Titania as a Semiconductor Ligand

HORST KISCH

I. Introduction. . . . . . . . . . w • • • • 372 II. Titania-Chloroplatinum(IV) Complexes. . . . . 378

III. Titania-Halogenorhodium(III) Complexes (X=CI, Br) 384 IV. Summary and Outlook. . . . . . . . 391

Acknowledgments 391 References . . . . . . . . . . . . 392

viii

I f

CONTENTS

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

VI. Crystal Structures. . . . . . 37 VII. Reaction Mechanism . . . . . . . . . 42

VIII. Wider Comparisons with Other Heme Enzymes . 46 IX. Concluding Remarks . . . . . . . . 48

Acknowledgment . 49 References. . . . . . . . . . . 49

v

VI CONTENTS

Reactivity of Manganese Superoxide Dismutase Mimics Toward Superoxide and Nitric Oxide: Selectivity Versus Cross-Reactivity

IVANA IVANOVIC-BuRMAZOVIC and MILOS R. FILIPOVIC

I. General Facts About Superoxide . . . . . . . . . II. Life with Superoxide. . . . . . . . . . . . .

III. Manganese Superoxide Dismutase Mimetics (MnSODm) IV. Some Methodological, Mechanistic, and Cross-reactivity

Consideration. . . . . . . . . . . . . . V. Manganese SOD Enzymes and Reactive Nitrogen

Species: Cross-reactivity, Not Selectivity. . VI. ROS Versus RNS. . . . . . . . . .

VII. Reaction of SOD Mimics with Peroxynitrite .

54 57 60

65

76 77 79

VIII. Reaction of MnSOD Mimics with NO. IX. Conclusion and Perspectives . . . .

Acknowledgment . References . . . . . . . . . . .

. . 82

. . 89 90

. . 90

Azanone (HNO) Interaction with Hemeproteins and Metalloporphyrins

FABIO DOCTOROVICH, DAMIAN E. BIKIEL, JUAN PELLEGRINO,

SEBASTIAN A. SUAREZ and MARCELO A. MARTI

I. Introduction: Chemistry and Biology of Azanone. . . ., 98 II. Azanone Reactivity with Hemeproteins and Metalloporphyrins 108

III. Azanone Detection with Metalloporphyrins and Heme Proteins 129 IV. Conclusions . . . . . . . . . . 134

Acknowledgments 135 References . . . . . . . . . . 135

Advances in the Mechanistic Understanding of Selected Reactions of Transition Metal Polyaminecarboxylate Complexes

ARIANE BRAUSAM and RUDI VAN ELDIK

I. Introduction . . . . . . . . . . . . . . . 142 II. Water-Exchange Reactions on [M(L)HzOl Complexes

(M=FeIIIlII,MnII) . . . . . . . . . . . . . . 147 III. Water-Exchange Reactions on [Ni(L)HzOl Complexes 155 IV. Binding of Nitric Oxide to [FeII(edta)(HzO)]z~ 159 V. Binding of Nitric Oxide to [RuIII(edta)(HzO)]-. . . 163

co:

VI. Binding of Hydrogen Peroxide VII. Binding of Hydrogen Peroxide

VIII. Conclusions . . . . . Acknowledgments References . . . . . .

Polyaminecarboxylaterutheni of Bioinorganic Reactions.

DEBABRATA CHA'ITEF

I. Introduction. . . . . . II. Background Chemistry. .

III. Substitution of Ru(III)-pac COIl IV. Reactions of RullI_pac Comple~ V. Reactions of Rulll-pac Comple~

Biomolecules. . . . . . VI. Reactions of Ru-pac Complexe!

VII. Reaction of Rulll-pac ComplexE Oxidants and Reductanl:.'>

VIII. Concluding Remarks . Acknowledgments References . . . . .

The Chemistry of Monovale

ARIELA BURG a

I. Introduction. . . . . . II. Cu(l) in Aqueous Solutions .

III. Cu(I)L" as a Reducing Agent IV. Catalysis . . . . . . . . V. Summary.

References . . . . .

Hypo

MICRA

I. Introduction. . . . . . II. Molecular Structure, PropertiE

III. Reaction Mechanisms . . .

ard vity

54 57 60

65

76 77 79 82 89 90 90

hyrins

98 108 129 134 135 135

tions

142

147 155 159 163

CONTENTS Vll

VI. Binding of Hydrogen Peroxide to FeIII(L) Complexes 165 VII. Binding of Hydrogen Peroxide to [RuIII(edta)(H20)]­ 168

VIII. Conclusions. . . 176 Acknowledgments 178 References . . . . 179

Polyaminecarboxylateruthenium(llI) Complexes on the Mosaic of Bioinorganic Reactions. Kinetic and Mechanistic Impact

DEBABRATA CHATTERJEE and RUDI VAN ELDIK

I. Introduction. . . . . . . . . . 184 II. Background Chemistry. . . . . . 184

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

Biomolecules . . . . . . . . . . . . . . . . 193 VI. Reactions of Ru-pac Complexes Involving NO. . . . 199

VII. Reaction of RuIII-pac Complexes with Biologically Important Oxidants and Reductants 207

VIII. Concluding Remarks 213 Acknowledgments 214 References . . . . 214

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