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