Inorganic Aspects of Biological and Organic Chemistry
- 1st Edition - December 2, 2012
- Imprint: Academic Press
- Author: Robert Hanzlik
- Language: English
- Paperback ISBN:9 7 8 - 0 - 1 2 - 4 3 1 3 1 5 - 6
- eBook ISBN:9 7 8 - 0 - 3 2 3 - 1 5 1 1 6 - 0
Inorganic Aspects of Biological and Organic Chemistry investigates the inorganic aspects of biological and organic chemistry. Topics include the inorganic chemistry of group Ia and… Read more
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Request a sales quoteInorganic Aspects of Biological and Organic Chemistry investigates the inorganic aspects of biological and organic chemistry. Topics include the inorganic chemistry of group Ia and IIa metals; complexes of Ia and IIa cations in organic and biological chemistry; atomic structure and structure-activity correlations; and bonding in ligands and metal complexes. Ligand exchange reactions and factors in complex stability are also discussed. Comprised of 12 chapters, this book begins with an overview of some of the important roles of metals in biological and organic chemistry, followed by an analysis of the inorganic chemistry of group Ia and IIa metals. Complexes of Ia and IIa cations in organic and biological chemistry are then described, together with atomic structure and structure-activity correlations. Subsequent chapters deal with bonding in ligands and metal complexes; ligand exchange reactions and factors in complex stability; redox potentials and processes; and the influence of metal ions on equilibria. The book also considers catalysis by metal ions, metal complexes, and metalloenzymes before concluding with a chapter that examines the reactions of ligands in organometallic complexes. This monograph is written for teachers, students, and practitioners of organic, biological, and inorganic chemistry.
Preface
Periodic Table
I Introduction
Metals in Biological Chemistry
Metals in Organic Chemistry
General References
II Inorganic Chemistry of Group Ia and IIa Metals
Chemistry of Ia and IIa Metals
Structures of Ia and IIa Atoms and Ions
Influence of Ionization Potential on Chemical Properties
Dissolution of Crystal Lattices and Hydration of Cations
Water Structure
Solute Effects on Water Structure
Complexation of Ia and IIa Cations
References
III Complexes of Ia and IIa Cations in Organic and Biological Chemistry
Complex Cations in Organic Chemistry
Solubilization of Inorganic Reagents
Dissolving Metal Reductions
Carbanionic Reagents
Reactions of Metal Enolates
Resolution of Amines and Amino Acids
Metal-Macromolecule Interactions in Biology
Protein Structure
Isomorphous Substitution
Metal Ions and Biological Membranes
Real Membranes and Model Membranes
Models for Membrane Conductance
References
IV Atomic Structure and Structure—Activity Correlations
The Origins of Quantum Theory of Atomic Structure
Quantum Numbers and Atomic Orbitals
Quantum Numbers and Chemical Periodicity
Electronic Configurations and Hund's First Rule
Formation and Ligation of Transition Metal Ions and Implications for Organic and Biochemical Systems
References
V Bonding in Ligands and Metal Complexes
Concepts in Chemical Bonding
The Electron Pair Bond
Electronegativity
Valence Bond Theory and Covalent Bonding
Hybridization of Atomic Orbitals
Transition Metal Complexes
Crystal Field Theory
Crystal Field Splittings of d Orbital Energy Levels
The Jahn-Teller Effect
Molecular Orbital Theory
Molecular Orbital Energy Level Diagrams
Molecular Orbital Theory for Transition Metal Complexes
Chemical Consequences of Back-Bonding
The Eighteen-Electron Rule
References
VI Ligand Exchange Reactions and Factors in Complex Stability
Ligand Exchange Mechanisms
Ia and IIa Cations
Labile Transition Metal Complexes
Inert Transition Metal Complexes
Leaving and Entering Group Effects
Solvent Effects
Acid Catalysis and Metal Assistance in Solvolysis
Base-Catalyzed Solvolysis and Anchimeric Assistance
Ligand Exchange in Nonoctahedral Complexes
Factors Influencing the Stability of Metal Complexes
Metal Ion Properties
Ligand Properties
Bidentate Ligands and the Chelate Effect
Multidentate and Other Special Ligands
Mutual Metal—Ligand Effects in Complex Stability
Mixed Ligand Effects on Metal-Catalyzed Reactions
Preferred Binding Sites for Biologically Important Metals
References
VII Redox Potentials and Processes
Electrodes, Electromotive Forces, and Sign Conventions
Working with Redox Potentials
Equilibrium Constants
Stabilization of Particular Oxidation States of Metals
Factors Influencing the Redox Potential of Metals
Periodic Correlations
Ligand Effects
Redox Reactions of Water and Oxygen
Respiration: The Biological Reduction of Oxygen
Flavines and Pyridines
Quinones
Hemoproteins
Copper Redox Proteins
Nonheme Iron Proteins
Electron Transport and Oxidative Phosphorylation
Electron Transfer Mechanisms for Metals
Outer Sphere Reactions
Inner Sphere Reactions
Redox Reactions of Coordinated Ligands
Oxidations of Olefins by One- and Two-Electron Processes
Some Reactions Which Form or Consume Hydrogen Peroxide
References
VIII Influencing Equilibria with Metal Ions: Synthesis via Chelation
Metal-Directed Reactions
Chelation
Ligand Polarization
Template Effects
Redox Effects
Enantiomer Discrimination
Metal Ion Lability
Reactions of Schiff Base Ligand Systems
Metal-Directed Formation and Reactions of Enols
The Aldol Condensation and Related Equilibria
Carboxylation and Decarboxylation
Coordination Chemistry of Vitamin B6
Schiff Base Formation
α-Carbon Enolization and Subsequent Reactions
Other Reactions Involving Pyridoxal
Acid-Base Equilibria: Acidity of Coordinated Water
Optical Resolution of Amino Acids
References
IX Catalysis by Metal Ions, Metal Complexes, and Metalloenzymes
The Origin of Catalytic Effects
Survey of Metal-Catalyzed Reactions
Metal Enhancement of Leaving Group Reactivity
Solvolytic Reactions
Aconitase Action
Metal Catalysis via Ligand Polarization
Hydrolysis of Amino Acid Derivatives
Carboxypeptidase Action
Metal Catalysis via Template and Charge-Neutralization Effects
Reactions of Coordinated Nucleophiles
Carbonic Anhydrase Action
References
X Oxygen and Nitrogen
Binuclear μ-Peroxide and μ-Superoxide Complexes
Mononuclear Superoxide Complexes
Metal-Oxygen π Complexes
Oxygen Complexes in Biology
Hemerythrin and Hemocyanin
The Hemoglobin Problem
Coboglobins
Iron Complexes of Hindered Porphyrins
Preparation and Characterization of Dinitrogen Complexes
Reactions of Dinitrogen Complexes
Ruthenium and Osmium Amine Complexes
Cobalt and Iron Complexes
Molybdenum Dinitrogen Complexes
Titanium Dinitrogen Complexes
Chemical Nitrogen Fixation
Biological Nitrogen Fixation
References
XI Organometallic Complexes: Structure, Bonding, and Reaction Mechanisms
Ligands in Organometallic Chemistry
Transition Metal Hydrides
Transition Metal Alkyls
sp2—Carbon-Donor Ligands
Olefin and Acetylene Complexes
Carbonyl and Nitrosyl Complexes
Multielectron Ligands
Elementary Organometallic Reactions
1. Lewis Acid Dissociation-Association
2. Lewis Base Dissociation-Association
3. Oxidative Addition—Reductive Elimination
4. Insertion-Deinsertion
5. Oxidative Coupling-Reductive Decoupling
References
XII Reactions of Ligands in Organometallic Complexes
Factors Affecting Ligand Reactivity
Multidentate vs Multihapto Ligands
Ligand Polarization
Stereochemical Effects
Stabilization of Reactive Intermediates
Electrophilic and Nucleophilic Attack on Coordinated Ligands
Hückel Aromatic Ligands
η4-1,3-Diene, η3-Allyl, and η5-Pentadienyl Ligands
TT-Olefin, α-Alkyl, and η3-Allyl Ligands
Oxymetallation Reactions
Carbon-Carbon Coupling Reactions
Reductive Coupling of Organic Halides
Cyanation
Insertion Reactions of Olefins and Acetylenes
Carbonylation Reactions
Decarbonylation Reactions
Addition Reactions of Olefins and Acetylenes
Hydrogenation
Hydrozirconation
Catalysis of "Symmetry-Forbidden" Reactions
Hydrogen Migrations
Valence Bond Isomerizations
Olefin Metathesis
Stabilization and Transfer of Reactive Ligands
References
Subject Index
- Edition: 1
- Published: December 2, 2012
- Imprint: Academic Press
- Language: English
- Paperback ISBN: 9780124313156
- eBook ISBN: 9780323151160
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