Details

Spin States in Biochemistry and Inorganic Chemistry


Spin States in Biochemistry and Inorganic Chemistry

Influence on Structure and Reactivity
1. Aufl.

von: Marcel Swart, Miquel Costas

126,99 €

Verlag: Wiley
Format: PDF
Veröffentl.: 17.09.2015
ISBN/EAN: 9781118898307
Sprache: englisch
Anzahl Seiten: 472

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Beschreibungen

<p>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.</p> <p><i>Spin States in Biochemistry and Inorganic Chemistry</i> 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.</p> <p>Topics covered include:</p> <ul> <li>DFT and ab initio wavefunction approaches to spin states</li> <li>Experimental techniques for determining spin states</li> <li>Molecular discovery in spin crossover</li> <li>Multiple spin state scenarios in organometallic reactivity and gas phase reactions</li> <li>Transition-metal complexes involving redox non-innocent ligands</li> <li>Polynuclear iron sulfur clusters</li> <li>Molecular magnetism</li> <li>NMR analysis of spin densities</li> </ul> <p>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.</p>
<p>About the Editors xv</p> <p>List of Contributors xvii</p> <p>Foreword xxi</p> <p>Acknowledgments xxiii</p> <p><b>1 General Introduction to Spin States 1</b><br /><i>Marcel Swart and Miquel Costas</i></p> <p>1.1 Introduction 1</p> <p>1.2 Experimental Chemistry: Reactivity, Synthesis and Spectroscopy 2</p> <p>1.3 Computational Chemistry: Quantum Chemistry and Basis Sets 4</p> <p><b>2 Application of Density Functional and Density Functional Based Ligand Field Theory to Spin States 7</b><br /><i>Claude Daul, Matija Zlatar, Maja Gruden-Pavlovic and Marcel Swart</i></p> <p>2.1 Introduction 7</p> <p>2.2 What Is the Problem with Theory? 9</p> <p>2.2.1 Density Functional Theory 9</p> <p>2.2.2 LF Theory: Bridging the Gap Between Experimental and Computational Coordination Chemistry 11</p> <p>2.3 Validation and Application Studies 15</p> <p>2.3.1 Use of OPBE, SSB-D and S12g Density Functionals for Spin-State Splittings 17</p> <p>2.3.2 Application of LF-DFT 21</p> <p>2.4 Concluding Remarks 25</p> <p><b>3 Ab Initio Wavefunction Approaches to Spin States 35</b><br /><i>Carmen Sousa and Coen de Graaf</i></p> <p>3.1 Introduction and Scope 35</p> <p>3.2 Wavefunction-Based Methods for Spin States 35</p> <p>3.2.1 Single Reference Methods 36</p> <p>3.2.2 Multireference Methods 37</p> <p>3.2.3 MR Perturbation Theory 39</p> <p>3.2.4 Variational Approaches 40</p> <p>3.2.5 Density Matrix Renormalization Group Theory 40</p> <p>3.3 Spin Crossover 41</p> <p>3.3.1 Choice of Active Space and Basis Set 41</p> <p>3.3.2 The HS–LS Energy Difference 43</p> <p>3.3.3 Light-Induced Excited Spin State Trapping (LIESST) 45</p> <p>3.3.4 Spin Crossover in Other Metals 47</p> <p>3.4 Magnetic Coupling 47</p> <p>3.5 Spin States in Biochemical and Biomimetic Systems 50</p> <p>3.6 Two-State Reactivity 52</p> <p>3.7 Concluding Remarks 52</p> <p><b>4 Experimental Techniques for Determining Spin States 59</b><br /><i>Carole Duboc and Marcello Gennari</i></p> <p>4.1 Introduction 59</p> <p>4.2 Magnetic Measurements 61</p> <p>4.2.1 g-Anisotropy and Zero-Field Splitting (zfs) 64</p> <p>4.2.2 Unquenched Orbital Moment in the Ground State 64</p> <p>4.2.3 Exchange Interactions 64</p> <p>4.2.4 Spin Transitions and Spin Crossover 66</p> <p>4.3 EPR Spectroscopy 66</p> <p>4.4 Mössbauer Spectroscopy 70</p> <p>4.5 X-ray Spectroscopic Techniques 74</p> <p>4.6 NMR Spectroscopy 77</p> <p>4.7 Other Techniques 80</p> <p>4.A Appendix 81</p> <p>4.A.1 Theoretical Background 81</p> <p>4.A.2 List of Symbols 82</p> <p><b>5 Molecular Discovery in Spin Crossover 85</b><br /><i>Robert J. Deeth</i></p> <p>5.1 Introduction 85</p> <p>5.2 Theoretical Background 85</p> <p>5.2.1 Spin Transition Curves 88</p> <p>5.2.2 Light-Induced Excited Spin State Trapping 89</p> <p>5.3 Thermal SCO Systems: Fe(II) 90</p> <p>5.4 SCO in Non-d6 Systems 93</p> <p>5.5 Computational Methods 95</p> <p>5.6 Outlook 98</p> <p><b>6 Multiple Spin-State Scenarios in Organometallic Reactivity 103</b><br /><i>Wojciech I. Dzik, Wesley Böhmer and Bas de Bruin</i></p> <p>6.1 Introduction 103</p> <p>6.2 "Spin-Forbidden" Reactions and Two-State Reactivity 104</p> <p>6.3 Spin-State Changes in Transition Metal Complexes 107</p> <p>6.3.1 Influence of the Spin State on the Kinetics of Ligand Exchange 108</p> <p>6.3.2 Stoichiometric Bond Making and Breaking Reactions 109</p> <p>6.3.3 Spin-State Situations Involving Redox-Active Ligands 115</p> <p>6.4 Spin-State Changes in Catalysis 119</p> <p>6.4.1 Catalytic (Cyclo)oligomerizations 119</p> <p>6.4.2 Phillips Cr(II)/SiO2 Catalyst 121</p> <p>6.4.3 SNS–CrCl3 Catalyst 123</p> <p>6.5 Concluding Remarks 125</p> <p><b>7 Principles and Prospects of Spin-States Reactivity in Chemistry and Bioinorganic Chemistry 131</b><br /><i>Dandamudi Usharani, Binju Wang, Dina A. Sharon and Sason Shaik</i></p> <p>7.1 Introduction 131</p> <p>7.2 Spin-States Reactivity 132</p> <p>7.2.1 Two-State and Multi-State Reactivity 133</p> <p>7.2.2 Origins of Spin-Selective Reactivity: Exchange-Enhanced Reactivity and Orbital Selection Rules 137</p> <p>7.2.3 Considerations of Exchange-Enhanced Reactivity versus Orbital-Controlled Reactivity 140</p> <p>7.2.4 Consideration of Spin-State Selectivity in H-Abstraction: The Power of EER 142</p> <p>7.2.5 The Origins of Mechanistic Selection – Why Are C–H Hydroxylations Stepwise Processes? 146</p> <p>7.3 Prospects of Two-State Reactivity and Multi-State Reactivity 148</p> <p>7.3.1 Probing Spin-State Reactivity 148</p> <p>7.3.2 Are Spin Inversion Probabilities Useful for Analyzing TSR? 150</p> <p>7.4 Concluding Remarks 151</p> <p><b>8 Multiple Spin-State Scenarios in Gas-Phase Reactions 157</b><br /><i>Jana Roithová</i></p> <p>8.1 Introduction 157</p> <p>8.2 Experimental Methods for the Investigation of Metal-Ion Reactions 158</p> <p>8.3 Multiple State Reactivity: Reactions of Metal Cations with Methane 160</p> <p>8.4 Effect of the Oxidation State: Reactions of Metal Hydride Cations with Methane 163</p> <p>8.5 Two-State Reactivity: Reactions of Metal Oxide Cations 164</p> <p>8.6 Effect of Ligands 171</p> <p>8.7 Effect of Noninnocent Ligands 174</p> <p>8.8 Concluding Remarks 177</p> <p><b>9 Catalytic Function and Mechanism of Heme and Nonheme Iron(IV)–Oxo Complexes in Nature 185</b><br /><i>Matthew G. Quesne, Abayomi S. Faponle, David P. Goldberg and Sam P. de Visser</i></p> <p>9.1 Introduction 185</p> <p>9.2 Cytochrome P450 Enzymes 186</p> <p>9.2.1 Importance of Cytochrome P450 Enzymes 187</p> <p>9.2.2 P450 Activation of Long-Chain Fatty Acids 188</p> <p>9.2.3 Heme Monooxygenases and Peroxygenases 188</p> <p>9.2.4 Catalytic Cycle of Cytochrome P450 Enzymes 188</p> <p>9.3 Nonheme Iron Dioxygenases 190</p> <p>9.3.1 Cysteine Dioxygenase 191</p> <p>9.3.2 AlkB Repair Enzymes 192</p> <p>9.3.3 Nonheme Iron Halogenases 194</p> <p>9.4 Conclusions 197</p> <p>9.5 Acknowledgments 197</p> <p><b>10 Terminal Metal–Oxo Species with Unusual Spin States 203</b><br /><i>Sarah A. Cook, David C. Lacy and Andy S. Borovik</i></p> <p>10.1 Introduction 203</p> <p>10.2 Bonding 204</p> <p>10.2.1 Bonding Considerations: Tetragonal Symmetry 204</p> <p>10.2.2 Bonding Considerations: Trigonal Symmetry 205</p> <p>10.2.3 Methods of Characterization 206</p> <p>10.3 Case Studies 206</p> <p>10.3.1 Iron–Oxo Chemistry 206</p> <p>10.3.2 Manganese–Oxo Chemistry 212</p> <p>10.3.3 Cautionary Tales: Late Transition Metal Oxido Complexes 217</p> <p>10.3.4 Effects of Redox Inactive Metal Ions 217</p> <p>10.3.5 Metal–Oxyl Complexes 218</p> <p>10.4 Reactivity 218</p> <p>10.4.1 General Concepts: Proton versus Electron Transfer 218</p> <p>10.4.2 Spin State and Reactivity 220</p> <p>10.5 Summary 220</p> <p><b>11 Multiple Spin Scenarios in Transition-Metal Complexes Involving Redox Non-Innocent Ligands 229</b><br /><i>Florian Heims and Kallol Ray</i></p> <p>11.1 Introduction 229</p> <p>11.2 Survey of Non-Innocent Ligands 231</p> <p>11.3 Identification of Non-Innocent Ligands 232</p> <p>11.3.1 X-ray Crystallography 232</p> <p>11.3.2 EPR Spectroscopy 234</p> <p>11.3.3 Mössbauer Spectroscopy 235</p> <p>11.3.4 XAS Spectroscopy 236</p> <p>11.4 Selected Examples of Biological and Chemical Systems Involving Non-Innocent Ligands 237</p> <p>11.4.1 Copper–Radical Interaction 237</p> <p>11.4.2 Iron–Radical Interaction 246</p> <p>11.5 Concluding Remarks 252</p> <p><b>12 Molecular Magnetism 263</b><br /><i>Guillem Aromí, Patrick Gamez and Olivier Roubeau</i></p> <p>12.1 Introduction 263</p> <p>12.2 Molecular Magnetism: Motivations, Early Achievements and Foundations 264</p> <p>12.3 Molecular Nanomagnets (MNM) 265</p> <p>12.3.1 Single-Molecule Magnets 266</p> <p>12.3.2 Single-Chain Magnets (SCM) 268</p> <p>12.3.3 Single-Ion Magnets (SIM) 271</p> <p>12.4 Switchable Systems 273</p> <p>12.4.1 Spin Crossover (SCO) 273</p> <p>12.4.2 Valence Tautomerism (VT) 273</p> <p>12.4.3 Charge Transfer (CT) 275</p> <p>12.4.4 Light-Driven Ligand-Induced Spin Change (LD-LISC) 276</p> <p>12.4.5 Photoswitching (PS) Through Intermetallic CT 277</p> <p>12.5 Molecular-Based Magnetic Refrigerants 278</p> <p>12.5.1 The Magneto-Caloric Effect, Its Experimental Determination and Key Parameters 278</p> <p>12.5.2 Molecular to Extended Framework Coolers Towards Applications 280</p> <p>12.6 Quantum Manipulation of the Electronic Spin for Quantum Computing 282</p> <p>12.6.1 Organic Radicals 283</p> <p>12.6.2 Transition Metal Clusters 284</p> <p>12.6.3 Lanthanides as Realization of Qubits 285</p> <p>12.6.4 Engineering of Molecular Quantum Gates with Lanthanide Qubits 285</p> <p>12.7 Perspectives Toward Applications and Concluding Remarks 287</p> <p><b>13 Electronic Structure, Bonding, Spin Coupling, and Energetics of Polynuclear Iron–Sulfur Clusters – A Broken Symmetry Density Functional Theory Perspective 297</b><br /><i>Kathrin H. Hopmann, Vladimir Pelmenschikov, Wen-Ge Han Du and Louis Noodleman</i></p> <p>13.1 Introduction 297</p> <p>13.2 Iron–Sulfur Coordination: Geometric and Electronic Structure 298</p> <p>13.3 Spin Polarization Splitting and the Inverted Level Scheme 300</p> <p>13.4 Spin Coupling and the Broken Symmetry Method 300</p> <p>13.5 Electron Localization and Delocalization 301</p> <p>13.6 Polynuclear Systems – Competing Heisenberg Interactions and Spin-Dependent Delocalization 303</p> <p>13.7 Preamble to Three Major Topics: Iron–Sulfur–Nitrosyls, Adenosine-5'-Phosphosulfate Reductase, and the Proximal Cluster of Membrane-Bound [NiFe]-Hydrogenase 303</p> <p>13.7.1 Nonheme Iron Nitrosyl Complexes 303</p> <p>13.7.2 Adenosine-5'-Phosphosulfate Reductase 310</p> <p>13.7.3 Proximal Cluster of O2-Tolerant Membrane-Bound [NiFe]-Hydrogenase in Three Redox States 315</p> <p>13.8 Concluding Remarks 318</p> <p>13.9 Acknowledgments 319</p> <p><b>14 Environment Effects on Spin States, Properties, and Dynamics from Multi-level QM/MM Studies 327</b><br /><i>Alexander Petrenko and Matthias Stein</i></p> <p>14.1 Introduction 327</p> <p>14.1.1 Environmental Effects 328</p> <p>14.1.2 Hybrid QM/MM Embedding Schemes 329</p> <p>14.2 The Quantum Spin Hamiltonian – Linking Theory and Experiment 332</p> <p>14.3 The Solvent as an Environment 335</p> <p>14.3.1 Fourier Transform Infrared Spectroscopy 336</p> <p>14.3.2 Nuclear Magnetic Resonance 336</p> <p>14.3.3 Electron Paramagnetic Resonance 336</p> <p>14.4 Effect of Different Levels of QM and MM Treatment 338</p> <p>14.4.1 Convergence and Caveats at the QM Level 338</p> <p>14.4.2 Accuracy of the MM Part 341</p> <p>14.4.3 QM versus QM/MM Methods 341</p> <p>14.5 Illustrative Bioinorganic Examples 343</p> <p>14.5.1 Cytochrome P450 343</p> <p>14.5.2 Hydrogenase Enzymes 349</p> <p>14.5.3 Photosystem II and the Effect of QM Size 354</p> <p>14.6 From Static Spin-State Properties to Dynamics and Kinetics of Electron Transfer 357</p> <p>14.7 Final Remarks and Conclusions 359</p> <p>14.8 Acknowledgments 362</p> <p><b>15 High-Spin and Low-Spin States in {FeNO}7, FeIV=O, and FeIII–OOH Complexes and Their Correlations to Reactivity 369</b><br /><i>Edward I. Solomon, Kyle D. Sutherlin and Martin Srnec</i></p> <p>15.1 Introduction 369</p> <p>15.2 High- and Low-Spin {FeNO}7 Complexes: Correlations to O2 Activation 372</p> <p>15.2.1 Spectroscopic Definition of the Electronic Structure of High-Spin {FeNO}7 372</p> <p>15.2.2 Computational Studies of S = 3/2 {FeNO}7 Complexes and Related {FeO2}8 Complexes 375</p> <p>15.2.3 Extension to IPNS and HPPD: Implications for Reactivity 377</p> <p>15.2.4 Correlation to {FeNO}7 S = 1/2 385</p> <p>15.3 Low-Spin (S = 1) and High-Spin (S = 2) FeIV=O Complexes 386</p> <p>15.3.1 FeIV=O S = 1 Complexes: π* FMO 386</p> <p>15.3.2 FeIV=O S = 2 Sites: π* and σ* FMOs 390</p> <p>15.3.3 Contributions of FMOs to Reactivity 392</p> <p>15.4 Low-Spin (S = 1/2) and High-Spin (S = 5/2) FeIII–OOH Complexes 396</p> <p>15.4.1 Spin State Dependence of O–O Bond Homolysis 396</p> <p>15.4.2 FeIII–OOH S = 1/2 Reactivity: ABLM 398</p> <p>15.4.3 FeIII–OOH Spin State-Dependent Reactivity: FMOs 399</p> <p>15.5 Concluding Remarks 401</p> <p>15.6 Acknowledgments 402</p> <p><b>16 NMR Analysis of Spin Densities 409</b><br /><i>Kara L. Bren</i></p> <p>16.1 Introduction and Scope 409</p> <p>16.2 Spin Density Distribution in Transition Metal Complexes 410</p> <p>16.3 NMR of Paramagnetic Molecules 412</p> <p>16.3.1 Chemical Shifts 413</p> <p>16.3.2 Relaxation Rates 414</p> <p>16.4 Analysis of Spin Densities by NMR 416</p> <p>16.4.1 Factoring Contributions to Hyperfine Shifts 416</p> <p>16.4.2 Relaxation Properties and Spin Density 418</p> <p>16.4.3 DFT Approaches to Analyzing Hyperfine Shifts 419</p> <p>16.4.4 Natural Bond Orbital Analysis 420</p> <p>16.4.5 Application and Practicalities 421</p> <p>16.5 Probing Spin Densities in Paramagnetic Metalloproteins 422</p> <p>16.5.1 Heme Proteins 422</p> <p>16.5.2 Iron-Sulfur Proteins 425</p> <p>16.5.3 Copper Proteins 427</p> <p>16.6 Conclusions and Outlook 429</p> <p><b>17 Summary and Outlook 435</b><br /><i>Miquel Costas and Marcel Swart</i></p> <p>17.1 Summary 435</p> <p>17.2 Outlook 436</p> <p>Index 439</p>
"Spin States in Biochemistry and Inorganic Chemistry: Influence on Structure and Reactivity, edited by Marcel Swart and Miquel Costas is impressive testimony to the advances in theory, computations, and experiment, especially regarding transition metals in recent years, and a revealing look at how much remains to be developed....The authors provide detailed comparison of various computational methods with each other and with experimental data in many cases. Each chapter is an extensively referenced focused review article.  Chapters 1-3 emphasize computational methods....No single monograph can encompass a topic as broad as the title of this book, which is almost the entire chemistry of the periodic table.  However, for the selected topics, the volume provides a very valuable concise snapshot of the field.Computational chemistry for compounds of CHNO have advanced to the point that many experimentalists can routinely apply standard methods in Gaussian and other such programs with confidence, guided only by the state of the art described in other publications.  This book shows that in spite of enormous effort related to transition metal energy states and spin states, even the expert computational chemists need to proceed with caution and compare many functionals"- <b>(Gareth Eaton- December 2016)</b>
<p><b>Prof. Dr. Marcel Swart, Universitat de Girona, Spain</b><br />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.<br />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.</p> <p><b>Prof. Dr. Miquel Costas, Universitat de Girona, Spain</b><br />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.</p>
<p>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.</p> <p><i>Spin States in Biochemistry and Inorganic Chemistry</i> 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.</p> <p>Topics covered include:<br />• DFT and ab initio wavefunction approaches to spin states <br />• Experimental techniques for determining spin states<br />• Molecular discovery in spin crossover <br />• Multiple spin state scenarios in organometallic reactivity and gas phase reactions<br />• Transition-metal complexes involving redox non-innocent ligands<br />• Polynuclear iron sulfur clusters<br />• Molecular magnetism<br />• NMR analysis of spin densities</p> <p>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.</p>

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