Inorganic Aspects of Biological and Organic Chemistry

Inorganic Aspects of Biological and Organic Chemistry

1st Edition - January 28, 1976

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  • Author: Robert Hanzlik
  • eBook ISBN: 9780323151160

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Description

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 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.

Table of Contents


  • 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

Product details

  • No. of pages: 420
  • Language: English
  • Copyright: © Academic Press 1976
  • Published: January 28, 1976
  • Imprint: Academic Press
  • eBook ISBN: 9780323151160

About the Author

Robert Hanzlik

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