Professor David Rankin, School of Chemistry, University of Edinburgh, Scotland.Prof. Dr. Norbert W. Mitzel, Department for Inorganic Chemistry and Structural Chemistry, Bielefeld University, Germany.Dr Carole Morrison, School of Chemistry, University of Edinburgh, Scotland.

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• Preface xiiiCompanionWebsite xvAcknowledgements xviiBiographies xix1. Determining Structures – How and Why 11.1 Structural chemistry – where did it come from? 11.2 Asking questions about structure 41.3 Answering questions about structure 51.4 Plan of the book 71.5 Supplementary information 82. Tools and Concepts 92.1 Introduction 92.2 How structural chemistry techniques work 102.3 Symmetry 112.4 Electron density 212.5 Potential-energy surfaces 212.6 Timescales 242.7 Structural definitions 262.8 Sample preparation 272.9 Quantitative measurements 302.10 Instrumentation 322.11 Data analysis 363. Theoretical Methods 453.1 Introduction 453.2 Approximating the multi-electron Schrodinger equation 463.3 Exploring the potential-energy surface 523.4 Extending the computational model to the solid state 563.5 Calculating thermodynamic properties 613.6 Calculating properties of chemical bonding 633.7 Comparing theory with experiment: geometry 653.8 Comparing theory with experiment: molecular properties 683.9 Combining theory and experiment 744. Nuclear Magnetic Resonance Spectroscopy 794.1 Introduction 794.2 The nuclear magnetic resonance phenomenon 794.3 Experimental set-up 834.4 The pulse technique 864.5 Information from chemical shifts 924.6 Information from NMR signal intensities. 1004.7 Simple splitting patterns due to coupling between nuclear spins 1014.8 Information from coupling constants 1124.9 Not-so-simple spectra 1164.10 The multi-nuclear approach 1204.11 Multiple resonance 1214.12 Multi-pulse methods 1264.13 Two-dimensional NMR spectroscopy 1294.14 Gases 1404.15 Liquid crystals 1404.16 Solids 1414.17 Monitoring dynamic phenomena and reactions 1474.18 Paramagnetic compounds 1545. Electron Paramagnetic Resonance Spectroscopy 1695.1 The electron paramagnetic resonance experiment 1695.2 Hyperfine coupling in isotropic systems 1715.3 Anisotropic systems 1755.4 Transition-metal complexes 1795.5 Multiple resonance 1826. Mossbauer Spectroscopy 1896.1 Introduction 1896.2 The Mossbauer effect 1896.3 Experimental arrangements 1926.4 Information from Mossbauer spectroscopy 1946.5 Compound identification 2046.6 Temperature- and time-dependent effects 2086.7 Common difficulties encountered in Mossbauer spectroscopy 2126.8 Further possibilities in Mossbauer spectroscopy 2137. Rotational Spectra and Rotational Structure 2197.1 Introduction 2197.2 The rotation of molecules 2197.3 Rotational selection rules 2247.4 Instrumentation 2287.5 Using the information in a spectrum 2297.6 Using rotation constants to define molecular structures 2328. Vibrational Spectroscopy 2378.1 Introduction 2378.2 The physical basis; molecular vibrations 2378.3 Observing molecular vibrations 2398.4 Effects of phase on spectra 2458.5 Vibrational spectra and symmetry 2488.6 Assignment of bands to vibrations 2548.7 Complete empirical assignment of vibrational spectra 2628.8 Information from vibrational spectra 2638.9 Normal coordinate analysis 2729. Electronic Characterization Techniques 2779.1 Introduction 2779.2 Electron energy levels in molecules 2789.3 Symmetry and molecular orbitals 2799.4 Photoelectron spectroscopy 2819.5 Valence excitation spectroscopy 2869.6 Electronic energy levels and transitions in transition-metal complexes 2899.7 Circular dichroism 29810. Diffraction Methods 30310.1 Introduction 30310.2 Diffraction of electrons, neutrons and X-rays 30410.3 Diffraction by gases 30810.4 Diffraction by liquids 32110.5 Diffraction by single crystals; symmetry 32310.6 Diffraction by single crystals; the theoretical basis 32910.7 Diffraction by single crystals; the experiment. 33310.8 Diffraction by single crystals; interpretation of results 34110.9 Diffraction by single crystals; electron density determination 34910.10 Topological features of the electron density 35210.11 Phase dependence of molecular structures 36310.12 Diffraction of neutrons by crystals 36510.13 Diffraction by powders 36810.14 High-pressure crystallography 36810.15 Extended X-ray absorption fine structure 37111. Mass Spectrometry 38311.1 Introduction 38311.2 Experimental arrangements 38311.3 Data analysis 38711.4 Combined mass spectrometry methods 39212. Case Histories 39912.1 Introduction 39912.2 Xenon compounds 40012.3 The structure of N2O3 40712.4 Bismuthine 40912.5 Tetrahydroborates 41012.6 Is beryllocene a sandwich compound? 41512.7 Silylium cations – free at last 41812.8 True phosphinous acids 42212.9 Dihydrogen and dihydride complexes 42512.10 Agostic interactions: alkyl hydrogen atoms binding to metal atoms 42812.11 Lower symmetry than expected in some phosphines and phosphoranes 43012.12 Three-membered rings with dative bonds? 43212.13 Stable radicals 43612.14 Induced proton transfer in an adduct of squaric acid and bipyridine 44112.15 High-pressure studies of metal organic framework materials 44312.16 Mistaken identity: mono-coordinate copper(I) and silver(I) complexes 44612.17 Oxidation states in a palladium–tin complex 44712.18 Structural and spectroscopic consequences of a chemical change in an iron complex 45012.19 Some metalloproteins 45412.20 Atoms inside fullerene cages 45912.21 Structural chemistry – where is it going? 463Discussion problem 464References 464Index 467

Professor David Rankin, School of Chemistry, University of Edinburgh, Scotland.Prof. Dr. Norbert W. Mitzel, Department for Inorganic Chemistry and Structural Chemistry, Bielefeld University, Germany.Dr Carole Morrison, School of Chemistry, University of Edinburgh, Scotland.

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• Preface xiiiCompanionWebsite xvAcknowledgements xviiBiographies xix1. Determining Structures – How and Why 11.1 Structural chemistry – where did it come from? 11.2 Asking questions about structure 41.3 Answering questions about structure 51.4 Plan of the book 71.5 Supplementary information 82. Tools and Concepts 92.1 Introduction 92.2 How structural chemistry techniques work 102.3 Symmetry 112.4 Electron density 212.5 Potential-energy surfaces 212.6 Timescales 242.7 Structural definitions 262.8 Sample preparation 272.9 Quantitative measurements 302.10 Instrumentation 322.11 Data analysis 363. Theoretical Methods 453.1 Introduction 453.2 Approximating the multi-electron Schrodinger equation 463.3 Exploring the potential-energy surface 523.4 Extending the computational model to the solid state 563.5 Calculating thermodynamic properties 613.6 Calculating properties of chemical bonding 633.7 Comparing theory with experiment: geometry 653.8 Comparing theory with experiment: molecular properties 683.9 Combining theory and experiment 744. Nuclear Magnetic Resonance Spectroscopy 794.1 Introduction 794.2 The nuclear magnetic resonance phenomenon 794.3 Experimental set-up 834.4 The pulse technique 864.5 Information from chemical shifts 924.6 Information from NMR signal intensities. 1004.7 Simple splitting patterns due to coupling between nuclear spins 1014.8 Information from coupling constants 1124.9 Not-so-simple spectra 1164.10 The multi-nuclear approach 1204.11 Multiple resonance 1214.12 Multi-pulse methods 1264.13 Two-dimensional NMR spectroscopy 1294.14 Gases 1404.15 Liquid crystals 1404.16 Solids 1414.17 Monitoring dynamic phenomena and reactions 1474.18 Paramagnetic compounds 1545. Electron Paramagnetic Resonance Spectroscopy 1695.1 The electron paramagnetic resonance experiment 1695.2 Hyperfine coupling in isotropic systems 1715.3 Anisotropic systems 1755.4 Transition-metal complexes 1795.5 Multiple resonance 1826. Mossbauer Spectroscopy 1896.1 Introduction 1896.2 The Mossbauer effect 1896.3 Experimental arrangements 1926.4 Information from Mossbauer spectroscopy 1946.5 Compound identification 2046.6 Temperature- and time-dependent effects 2086.7 Common difficulties encountered in Mossbauer spectroscopy 2126.8 Further possibilities in Mossbauer spectroscopy 2137. Rotational Spectra and Rotational Structure 2197.1 Introduction 2197.2 The rotation of molecules 2197.3 Rotational selection rules 2247.4 Instrumentation 2287.5 Using the information in a spectrum 2297.6 Using rotation constants to define molecular structures 2328. Vibrational Spectroscopy 2378.1 Introduction 2378.2 The physical basis; molecular vibrations 2378.3 Observing molecular vibrations 2398.4 Effects of phase on spectra 2458.5 Vibrational spectra and symmetry 2488.6 Assignment of bands to vibrations 2548.7 Complete empirical assignment of vibrational spectra 2628.8 Information from vibrational spectra 2638.9 Normal coordinate analysis 2729. Electronic Characterization Techniques 2779.1 Introduction 2779.2 Electron energy levels in molecules 2789.3 Symmetry and molecular orbitals 2799.4 Photoelectron spectroscopy 2819.5 Valence excitation spectroscopy 2869.6 Electronic energy levels and transitions in transition-metal complexes 2899.7 Circular dichroism 29810. Diffraction Methods 30310.1 Introduction 30310.2 Diffraction of electrons, neutrons and X-rays 30410.3 Diffraction by gases 30810.4 Diffraction by liquids 32110.5 Diffraction by single crystals; symmetry 32310.6 Diffraction by single crystals; the theoretical basis 32910.7 Diffraction by single crystals; the experiment. 33310.8 Diffraction by single crystals; interpretation of results 34110.9 Diffraction by single crystals; electron density determination 34910.10 Topological features of the electron density 35210.11 Phase dependence of molecular structures 36310.12 Diffraction of neutrons by crystals 36510.13 Diffraction by powders 36810.14 High-pressure crystallography 36810.15 Extended X-ray absorption fine structure 37111. Mass Spectrometry 38311.1 Introduction 38311.2 Experimental arrangements 38311.3 Data analysis 38711.4 Combined mass spectrometry methods 39212. Case Histories 39912.1 Introduction 39912.2 Xenon compounds 40012.3 The structure of N2O3 40712.4 Bismuthine 40912.5 Tetrahydroborates 41012.6 Is beryllocene a sandwich compound? 41512.7 Silylium cations – free at last 41812.8 True phosphinous acids 42212.9 Dihydrogen and dihydride complexes 42512.10 Agostic interactions: alkyl hydrogen atoms binding to metal atoms 42812.11 Lower symmetry than expected in some phosphines and phosphoranes 43012.12 Three-membered rings with dative bonds? 43212.13 Stable radicals 43612.14 Induced proton transfer in an adduct of squaric acid and bipyridine 44112.15 High-pressure studies of metal organic framework materials 44312.16 Mistaken identity: mono-coordinate copper(I) and silver(I) complexes 44612.17 Oxidation states in a palladium–tin complex 44712.18 Structural and spectroscopic consequences of a chemical change in an iron complex 45012.19 Some metalloproteins 45412.20 Atoms inside fullerene cages 45912.21 Structural chemistry – where is it going? 463Discussion problem 464References 464Index 467

Professor David Rankin, School of Chemistry, University of Edinburgh, Scotland.Prof. Dr. Norbert W. Mitzel, Department for Inorganic Chemistry and Structural Chemistry, Bielefeld University, Germany.Dr Carole Morrison, School of Chemistry, University of Edinburgh, Scotland.

Select Guide Rating

• Preface xiiiCompanionWebsite xvAcknowledgements xviiBiographies xix1. Determining Structures – How and Why 11.1 Structural chemistry – where did it come from? 11.2 Asking questions about structure 41.3 Answering questions about structure 51.4 Plan of the book 71.5 Supplementary information 82. Tools and Concepts 92.1 Introduction 92.2 How structural chemistry techniques work 102.3 Symmetry 112.4 Electron density 212.5 Potential-energy surfaces 212.6 Timescales 242.7 Structural definitions 262.8 Sample preparation 272.9 Quantitative measurements 302.10 Instrumentation 322.11 Data analysis 363. Theoretical Methods 453.1 Introduction 453.2 Approximating the multi-electron Schrodinger equation 463.3 Exploring the potential-energy surface 523.4 Extending the computational model to the solid state 563.5 Calculating thermodynamic properties 613.6 Calculating properties of chemical bonding 633.7 Comparing theory with experiment: geometry 653.8 Comparing theory with experiment: molecular properties 683.9 Combining theory and experiment 744. Nuclear Magnetic Resonance Spectroscopy 794.1 Introduction 794.2 The nuclear magnetic resonance phenomenon 794.3 Experimental set-up 834.4 The pulse technique 864.5 Information from chemical shifts 924.6 Information from NMR signal intensities. 1004.7 Simple splitting patterns due to coupling between nuclear spins 1014.8 Information from coupling constants 1124.9 Not-so-simple spectra 1164.10 The multi-nuclear approach 1204.11 Multiple resonance 1214.12 Multi-pulse methods 1264.13 Two-dimensional NMR spectroscopy 1294.14 Gases 1404.15 Liquid crystals 1404.16 Solids 1414.17 Monitoring dynamic phenomena and reactions 1474.18 Paramagnetic compounds 1545. Electron Paramagnetic Resonance Spectroscopy 1695.1 The electron paramagnetic resonance experiment 1695.2 Hyperfine coupling in isotropic systems 1715.3 Anisotropic systems 1755.4 Transition-metal complexes 1795.5 Multiple resonance 1826. Mossbauer Spectroscopy 1896.1 Introduction 1896.2 The Mossbauer effect 1896.3 Experimental arrangements 1926.4 Information from Mossbauer spectroscopy 1946.5 Compound identification 2046.6 Temperature- and time-dependent effects 2086.7 Common difficulties encountered in Mossbauer spectroscopy 2126.8 Further possibilities in Mossbauer spectroscopy 2137. Rotational Spectra and Rotational Structure 2197.1 Introduction 2197.2 The rotation of molecules 2197.3 Rotational selection rules 2247.4 Instrumentation 2287.5 Using the information in a spectrum 2297.6 Using rotation constants to define molecular structures 2328. Vibrational Spectroscopy 2378.1 Introduction 2378.2 The physical basis; molecular vibrations 2378.3 Observing molecular vibrations 2398.4 Effects of phase on spectra 2458.5 Vibrational spectra and symmetry 2488.6 Assignment of bands to vibrations 2548.7 Complete empirical assignment of vibrational spectra 2628.8 Information from vibrational spectra 2638.9 Normal coordinate analysis 2729. Electronic Characterization Techniques 2779.1 Introduction 2779.2 Electron energy levels in molecules 2789.3 Symmetry and molecular orbitals 2799.4 Photoelectron spectroscopy 2819.5 Valence excitation spectroscopy 2869.6 Electronic energy levels and transitions in transition-metal complexes 2899.7 Circular dichroism 29810. Diffraction Methods 30310.1 Introduction 30310.2 Diffraction of electrons, neutrons and X-rays 30410.3 Diffraction by gases 30810.4 Diffraction by liquids 32110.5 Diffraction by single crystals; symmetry 32310.6 Diffraction by single crystals; the theoretical basis 32910.7 Diffraction by single crystals; the experiment. 33310.8 Diffraction by single crystals; interpretation of results 34110.9 Diffraction by single crystals; electron density determination 34910.10 Topological features of the electron density 35210.11 Phase dependence of molecular structures 36310.12 Diffraction of neutrons by crystals 36510.13 Diffraction by powders 36810.14 High-pressure crystallography 36810.15 Extended X-ray absorption fine structure 37111. Mass Spectrometry 38311.1 Introduction 38311.2 Experimental arrangements 38311.3 Data analysis 38711.4 Combined mass spectrometry methods 39212. Case Histories 39912.1 Introduction 39912.2 Xenon compounds 40012.3 The structure of N2O3 40712.4 Bismuthine 40912.5 Tetrahydroborates 41012.6 Is beryllocene a sandwich compound? 41512.7 Silylium cations – free at last 41812.8 True phosphinous acids 42212.9 Dihydrogen and dihydride complexes 42512.10 Agostic interactions: alkyl hydrogen atoms binding to metal atoms 42812.11 Lower symmetry than expected in some phosphines and phosphoranes 43012.12 Three-membered rings with dative bonds? 43212.13 Stable radicals 43612.14 Induced proton transfer in an adduct of squaric acid and bipyridine 44112.15 High-pressure studies of metal organic framework materials 44312.16 Mistaken identity: mono-coordinate copper(I) and silver(I) complexes 44612.17 Oxidation states in a palladium–tin complex 44712.18 Structural and spectroscopic consequences of a chemical change in an iron complex 45012.19 Some metalloproteins 45412.20 Atoms inside fullerene cages 45912.21 Structural chemistry – where is it going? 463Discussion problem 464References 464Index 467