Marcel Swart, Miquel Costas

Spin States in Biochemistry and Inorganic Chemistry

Influence on Structure and Reactivity

• Gebundenes Buch

Produktbeschreibung

It has long been recognized that metal spin states play a central role in the reactivity of important biomolecules, in industrial catalysis and in spin crossover compounds. As the fields of inorganic chemistry and catalysis move towards the use of cheap, non-toxic first row transition metals, it is essential to understand the important role of spin states in influencing molecular structure, bonding and reactivity. Spin States in Biochemistry and Inorganic Chemistry provides a complete picture on the importance of spin states for reactivity in biochemistry and inorganic chemistry, presenting both theoretical and experimental perspectives. The successes and pitfalls of theoretical methods such as DFT, ligand-field theory and coupled cluster theory are discussed, and these methods are applied in studies throughout the book. Important spectroscopic techniques to determine spin states in transition metal complexes and proteins are explained, and the use of NMR for the analysis of spin densities is described. Topics covered include: - DFT and ab initio wavefunction approaches to spin states - Experimental techniques for determining spin states - Molecular discovery in spin crossover - Multiple spin state scenarios in organometallic reactivity and gas phase reactions - Transition-metal complexes involving redox non-innocent ligands - Polynuclear iron sulfur clusters - Molecular magnetism - NMR analysis of spin densities This book is a valuable reference for researchers working in bioinorganic and inorganic chemistry, computational chemistry, organometallic chemistry, catalysis, spin-crossover materials, materials science, biophysics and pharmaceutical chemistry.

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Produktdetails

• Verlag: Wiley
• Seitenzahl: 480
• Erscheinungstermin: 14. Dezember 2015
• Englisch
• Abmessung: 255mm x 195mm x 30mm
• Gewicht: 990g
• ISBN-13: 9781118898314
• ISBN-10: 1118898311
• Artikelnr.: 42835233

Autorenporträt

Prof. Dr. Marcel Swart, Universitat de Girona, Spain Marcel Swart is ICREA Research Professor in the Institute of Computational Chemistry Catalysis at the Universitat de Girona, Spain. He is a computational/theoretical chemist working in the field of (bio)chemistry and biomedicine. He has published >100 papers in peer-reviewed scientific journals and has an h-index of 26. He was awarded the Young Scientist 2005 award by ICCMSE (International Conference of Computational Methods in Sciences and Engineering), and was selected as one of the promising young inorganic chemists of "The next generation" that were invited to contribute to a special issue of Inorganica Chimica Acta in 2007, and to a special issue of Polyhedron in 2010. In 2012, he was awarded the MGMS Silver Jubilee Prize "for his development of new computational chemistry programs, design of new research tools and application to (bio)chemical systems that are highly relevant for society and science." In September 2012 he organized a CECAM/ESF Workshop on "Spin states in biochemistry and inorganic chemistry", highlighted in Nature Chem. 2013, 5, 7-9. Prof. Dr. Miquel Costas, Universitat de Girona, Spain Miquel Costas became Professor Titular at the University of Girona in 2003. He has published over 70 papers in international journals that have received over 3470 citations. His research interests involve the study of transition metal complexes involved in challenging oxidative transformations, including functionalization of C-H bonds and water oxidation. These systems commonly operate in multistate reactivity scenarios, implicating multiple spin states.

Inhaltsangabe

About the Editors xv List of Contributors xvii Foreword xxi Acknowledgments xxiii 1 General Introduction to Spin States 1 Marcel Swart and Miquel Costas 1.1 Introduction 1 1.2 Experimental Chemistry: Reactivity, Synthesis and Spectroscopy 2 1.3 Computational Chemistry: Quantum Chemistry and Basis Sets 4 2 Application of Density Functional and Density Functional Based Ligand Field Theory to Spin States 7 Claude Daul, Matija Zlatar, Maja Gruden-Pavlovic and Marcel Swart 2.1 Introduction 7 2.2 What Is the Problem with Theory? 9 2.2.1 Density Functional Theory 9 2.2.2 LF Theory: Bridging the Gap Between Experimental and Computational Coordination Chemistry 11 2.3 Validation and Application Studies 15 2.3.1 Use of OPBE, SSB-D and S12g Density Functionals for Spin-State Splittings 17 2.3.2 Application of LF-DFT 21 2.4 Concluding Remarks 25 3 Ab Initio Wavefunction Approaches to Spin States 35 Carmen Sousa and Coen de Graaf 3.1 Introduction and Scope 35 3.2 Wavefunction-Based Methods for Spin States 35 3.2.1 Single Reference Methods 36 3.2.2 Multireference Methods 37 3.2.3 MR Perturbation Theory 39 3.2.4 Variational Approaches 40 3.2.5 Density Matrix Renormalization Group Theory 40 3.3 Spin Crossover 41 3.3.1 Choice of Active Space and Basis Set 41 3.3.2 The HS-LS Energy Difference 43 3.3.3 Light-Induced Excited Spin State Trapping (LIESST) 45 3.3.4 Spin Crossover in Other Metals 47 3.4 Magnetic Coupling 47 3.5 Spin States in Biochemical and Biomimetic Systems 50 3.6 Two-State Reactivity 52 3.7 Concluding Remarks 52 4 Experimental Techniques for Determining Spin States 59 Carole Duboc and Marcello Gennari 4.1 Introduction 59 4.2 Magnetic Measurements 61 4.2.1 g-Anisotropy and Zero-Field Splitting (zfs) 64 4.2.2 Unquenched Orbital Moment in the Ground State 64 4.2.3 Exchange Interactions 64 4.2.4 Spin Transitions and Spin Crossover 66 4.3 EPR Spectroscopy 66 4.4 Mössbauer Spectroscopy 70 4.5 X-ray Spectroscopic Techniques 74 4.6 NMR Spectroscopy 77 4.7 Other Techniques 80 4.A Appendix 81 4.A.1 Theoretical Background 81 4.A.2 List of Symbols 82 5 Molecular Discovery in Spin Crossover 85 Robert J. Deeth 5.1 Introduction 85 5.2 Theoretical Background 85 5.2.1 Spin Transition Curves 88 5.2.2 Light-Induced Excited Spin State Trapping 89 5.3 Thermal SCO Systems: Fe(II) 90 5.4 SCO in Non-d6 Systems 93 5.5 Computational Methods 95 5.6 Outlook 98 6 Multiple Spin-State Scenarios in Organometallic Reactivity 103 Wojciech I. Dzik, Wesley Böhmer and Bas de Bruin 6.1 Introduction 103 6.2 "Spin-Forbidden" Reactions and Two-State Reactivity 104 6.3 Spin-State Changes in Transition Metal Complexes 107 6.3.1 Influence of the Spin State on the Kinetics of Ligand Exchange 108 6.3.2 Stoichiometric Bond Making and Breaking Reactions 109 6.3.3 Spin-State Situations Involving Redox-Active Ligands 115 6.4 Spin-State Changes in Catalysis 119 6.4.1 Catalytic (Cyclo)oligomerizations 119 6.4.2 Phillips Cr(II)/SiO2 Catalyst 121 6.4.3 SNS-CrCl3 Catalyst 123 6.5 Concluding Remarks 125 7 Principles and Prospects of Spin-States Reactivity in Chemistry and Bioinorganic Chemistry 131 Dandamudi Usharani, Binju Wang, Dina A. Sharon and Sason Shaik 7.1 Introduction 131 7.2 Spin-States Reactivity 132 7.2.1 Two-State and Multi-State Reactivity 133 7.2.2 Origins of Spin-Selective Reactivity: Exchange-Enhanced Reactivity and Orbital Selection Rules 137 7.2.3 Considerations of Exchange-Enhanced Reactivity versus Orbital-Controlled Reactivity 140 7.2.4 Consideration of Spin-State Selectivity in H-Abstraction: The Power of EER 142 7.2.5 The Origins of Mechanistic Selection - Why Are C-H Hydroxylations Stepwise Processes? 146 7.3 Prospects of Two-State Reactivity and Multi-State Reactivity 148 7.3.1 Probing Spin-State Reactivity 148 7.3.2 Are Spin Inversion Probabilities Useful for Analyzing TSR? 150 7.4 Concluding Remarks 151 8 Multiple Spin-State Scenarios in Gas-Phase Reactions 157 Jana Roithová 8.1 Introduction 157 8.2 Experimental Methods for the Investigation of Metal-Ion Reactions 158 8.3 Multiple State Reactivity: Reactions of Metal Cations with Methane 160 8.4 Effect of the Oxidation State: Reactions of Metal Hydride Cations with Methane 163 8.5 Two-State Reactivity: Reactions of Metal Oxide Cations 164 8.6 Effect of Ligands 171 8.7 Effect of Noninnocent Ligands 174 8.8 Concluding Remarks 177 9 Catalytic Function and Mechanism of Heme and Nonheme Iron(IV)-Oxo Complexes in Nature 185 Matthew G. Quesne, Abayomi S. Faponle, David P. Goldberg and Sam P. de Visser 9.1 Introduction 185 9.2 Cytochrome P450 Enzymes 186 9.2.1 Importance of Cytochrome P450 Enzymes 187 9.2.2 P450 Activation of Long-Chain Fatty Acids 188 9.2.3 Heme Monooxygenases and Peroxygenases 188 9.2.4 Catalytic Cycle of Cytochrome P450 Enzymes 188 9.3 Nonheme Iron Dioxygenases 190 9.3.1 Cysteine Dioxygenase 191 9.3.2 AlkB Repair Enzymes 192 9.3.3 Nonheme Iron Halogenases 194 9.4 Conclusions 197 9.5 Acknowledgments 197 10 Terminal Metal-Oxo Species with Unusual Spin States 203 Sarah A. Cook, David C. Lacy and Andy S. Borovik 10.1 Introduction 203 10.2 Bonding 204 10.2.1 Bonding Considerations: Tetragonal Symmetry 204 10.2.2 Bonding Considerations: Trigonal Symmetry 205 10.2.3 Methods of Characterization 206 10.3 Case Studies 206 10.3.1 Iron-Oxo Chemistry 206 10.3.2 Manganese-Oxo Chemistry 212 10.3.3 Cautionary Tales: Late Transition Metal Oxido Complexes 217 10.3.4 Effects of Redox Inactive Metal Ions 217 10.3.5 Metal-Oxyl Complexes 218 10.4 Reactivity 218 10.4.1 General Concepts: Proton versus Electron Transfer 218 10.4.2 Spin State and Reactivity 220 10.5 Summary 220 11 Multiple Spin Scenarios in Transition-Metal Complexes Involving Redox Non-Innocent Ligands 229 Florian Heims and Kallol Ray 11.1 Introduction 229 11.2 Survey of Non-Innocent Ligands 231 11.3 Identification of Non-Innocent Ligands 232 11.3.1 X-ray Crystallography 232 11.3.2 EPR Spectroscopy 234 11.3.3 Mössbauer Spectroscopy 235 11.3.4 XAS Spectroscopy 236 11.4 Selected Examples of Biological and Chemical Systems Involving Non-Innocent Ligands 237 11.4.1 Copper-Radical Interaction 237 11.4.2 Iron-Radical Interaction 246 11.5 Concluding Remarks 252 12 Molecular Magnetism 263 Guillem Aromí, Patrick Gamez and Olivier Roubeau 12.1 Introduction 263 12.2 Molecular Magnetism: Motivations, Early Achievements and Foundations 264 12.3 Molecular Nanomagnets (MNM) 265 12.3.1 Single-Molecule Magnets 266 12.3.2 Single-Chain Magnets (SCM) 268 12.3.3 Single-Ion Magnets (SIM) 271 12.4 Switchable Systems 273 12.4.1 Spin Crossover (SCO) 273 12.4.2 Valence Tautomerism (VT) 273 12.4.3 Charge Transfer (CT) 275 12.4.4 Light-Driven Ligand-Induced Spin Change (LD-LISC) 276 12.4.5 Photoswitching (PS) Through Intermetallic CT 277 12.5 Molecular-Based Magnetic Refrigerants 278 12.5.1 The Magneto-Caloric Effect, Its Experimental Determination and Key Parameters 278 12.5.2 Molecular to Extended Framework Coolers Towards Applications 280 12.6 Quantum Manipulation of the Electronic Spin for Quantum Computing 282 12.6.1 Organic Radicals 283 12.6.2 Transition Metal Clusters 284 12.6.3 Lanthanides as Realization of Qubits 285 12.6.4 Engineering of Molecular Quantum Gates with Lanthanide Qubits 285 12.7 Perspectives Toward Applications and Concluding Remarks 287 13 Electronic Structure, Bonding, Spin Coupling, and Energetics of Polynuclear Iron-Sulfur Clusters - A Broken Symmetry Density Functional Theory Perspective 297 Kathrin H. Hopmann, Vladimir Pelmenschikov, Wen-Ge Han Du and Louis Noodleman 13.1 Introduction 297 13.2 Iron-Sulfur Coordination: Geometric and Electronic Structure 298 13.3 Spin Polarization Splitting and the Inverted Level Scheme 300 13.4 Spin Coupling and the Broken Symmetry Method 300 13.5 Electron Localization and Delocalization 301 13.6 Polynuclear Systems - Competing Heisenberg Interactions and Spin-Dependent Delocalization 303 13.7 Preamble to Three Major Topics: Iron-Sulfur-Nitrosyls, Adenosine-5'-Phosphosulfate Reductase, and the Proximal Cluster of Membrane-Bound [NiFe]-Hydrogenase 303 13.7.1 Nonheme Iron Nitrosyl Complexes 303 13.7.2 Adenosine-5'-Phosphosulfate Reductase 310 13.7.3 Proximal Cluster of O2-Tolerant Membrane-Bound [NiFe]-Hydrogenase in Three Redox States 315 13.8 Concluding Remarks 318 13.9 Acknowledgments 319 14 Environment Effects on Spin States, Properties, and Dynamics from Multi-level QM/MM Studies 327 Alexander Petrenko and Matthias Stein 14.1 Introduction 327 14.1.1 Environmental Effects 328 14.1.2 Hybrid QM/MM Embedding Schemes 329 14.2 The Quantum Spin Hamiltonian - Linking Theory and Experiment 332 14.3 The Solvent as an Environment 335 14.3.1 Fourier Transform Infrared Spectroscopy 336 14.3.2 Nuclear Magnetic Resonance 336 14.3.3 Electron Paramagnetic Resonance 336 14.4 Effect of Different Levels of QM and MM Treatment 338 14.4.1 Convergence and Caveats at the QM Level 338 14.4.2 Accuracy of the MM Part 341 14.4.3 QM versus QM/MM Methods 341 14.5 Illustrative Bioinorganic Examples 343 14.5.1 Cytochrome P450 343 14.5.2 Hydrogenase Enzymes 349 14.5.3 Photosystem II and the Effect of QM Size 354 14.6 From Static Spin-State Properties to Dynamics and Kinetics of Electron Transfer 357 14.7 Final Remarks and Conclusions 359 14.8 Acknowledgments 362 15 High-Spin and Low-Spin States in {FeNO}7, FeIV=O, and FeIII-OOH Complexes and Their Correlations to Reactivity 369 Edward I. Solomon, Kyle D. Sutherlin and Martin Srnec 15.1 Introduction 369 15.2 High- and Low-Spin {FeNO}7 Complexes: Correlations to O2 Activation 372 15.2.1 Spectroscopic Definition of the Electronic Structure of High-Spin {FeNO}7 372 15.2.2 Computational Studies of S = 3/2 {FeNO}7 Complexes and Related {FeO2}8 Complexes 375 15.2.3 Extension to IPNS and HPPD: Implications for Reactivity 377 15.2.4 Correlation to {FeNO}7 S = 1/2 385 15.3 Low-Spin (S = 1) and High-Spin (S = 2) FeIV=O Complexes 386 15.3.1 FeIV=O S = 1 Complexes:
* FMO 386 15.3.2 FeIV=O S = 2 Sites:
* and
* FMOs 390 15.3.3 Contributions of FMOs to Reactivity 392 15.4 Low-Spin (S = 1/2) and High-Spin (S = 5/2) FeIII-OOH Complexes 396 15.4.1 Spin State Dependence of O-O Bond Homolysis 396 15.4.2 FeIII-OOH S = 1/2 Reactivity: ABLM 398 15.4.3 FeIII-OOH Spin State-Dependent Reactivity: FMOs 399 15.5 Concluding Remarks 401 15.6 Acknowledgments 402 16 NMR Analysis of Spin Densities 409 Kara L. Bren 16.1 Introduction and Scope 409 16.2 Spin Density Distribution in Transition Metal Complexes 410 16.3 NMR of Paramagnetic Molecules 412 16.3.1 Chemical Shifts 413 16.3.2 Relaxation Rates 414 16.4 Analysis of Spin Densities by NMR 416 16.4.1 Factoring Contributions to Hyperfine Shifts 416 16.4.2 Relaxation Properties and Spin Density 418 16.4.3 DFT Approaches to Analyzing Hyperfine Shifts 419 16.4.4 Natural Bond Orbital Analysis 420 16.4.5 Application and Practicalities 421 16.5 Probing Spin Densities in Paramagnetic Metalloproteins 422 16.5.1 Heme Proteins 422 16.5.2 Iron-Sulfur Proteins 425 16.5.3 Copper Proteins 427 16.6 Conclusions and Outlook 429 17 Summary and Outlook 435 Miquel Costas and Marcel Swart 17.1 Summary 435 17.2 Outlook 436 Index 439