Inorganic Aspects of Biological and Organic 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