Organo Main Group Chemistry E-Book

Kin-ya Akiba

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 303

Veröffentlichungsjahr: 2011

Beschreibung

Forging a new association; main group elements and organic chemistry Covering the essentials of all main group elements in organic chemistry, along with the synthesis and reactions of their organic compounds in just one volume, Organo Main Group Chemistry breaks important new ground. While main group chemistry has traditionally been classified as part of inorganic chemistry, this book establishes the organic chemistry of main group elements for the first time. The organic compounds of elements in the second period of the periodic table, which are centered around carbon, are the major components of animals and plants, while those in the third period and below also play key roles worthy of discussion when studying main group element chemistry. The major chapters describe synthesis and reactivity of organic compounds in the third period and below and are arranged according to the order of the periodic table. Starting with the role of lithium and magnesium cations, the chapters reach fluorine and iodine compounds. The first two chapters summarize the unique and common characteristics of main group elements in relation to carbon. The latter chapters deal with modern topics that address the unique characteristics of organo main group compounds. Suitable for professional researchers, chemistry professors, and advanced students, Organo Main Group Chemistry presents a novel new approach to the way we view both main groups and organic chemistry itself.

Leseprobe

Table of Contents

Title Page

Copyright

Preface

Chapter 1: Main Group Elements and Heteroatoms: Scope and Characteristics

1.1 Aufbau Principle and Sign of Orbitals

1.2 Electronic Configuration of an Atom: Main Group Elements and Heteroatoms

1.3 Fundamental Properties of Main Group Elements

1.4 Acidity of Carboxylic Acid and Substituent Effect

1.5 Heteroatom Effect

References

Chapter 2: Main Group Element Effect

2.1 What is Main Group Element Effect?

2.2 Single Bond Energy and π–bond Energy

2.3 Hypervalent Compound

2.4 Effect of Hypervalent Bond (1): 3c–4e Bond and Structure

2.5 Effect of Hypervalent Bond (2): Apicophilicity and Pseudorotation

2.6 Effect of Hypervalent bond (3): Ligand Coupling Reaction (LCR) and Edge Inversion

2.7 Effect of σX−C

2.8 Effect of σ*X−C

References

Chapter 3: Lithium, Magnesium, and Copper Compounds

3.1 Synthesis

3.2 Structure

3.3 Reaction

References

Chapter 4: Boron and Aluminum Compounds

4.1 Synthesis

4.2 Structure

4.3 Reaction

References

Chapter 5: Silicon, Tin, and Lead Compounds

5.1 Synthesis

5.2 Reaction

5.3 Organotin and Lead Compounds

References

Chapter 6: Phosphorus, Antimony, and Bismuth Compounds

6.1 Phosphorus Compounds

6.2 Synthesis of Organophosphorus Compounds

6.3 Tertiary Phosphine and its Nucleophilic Reaction

6.4 Arbuzov Reaction

6.5 Perkow Reaction

6.6 Synthesis of Optically Active Phosphines

6.7 Ylide and Wittig Reaction and Related Ones

6.8 Reactions of Phosphonium Salts and Formation of Phosphoranes

6.9 Freezing BPR and its Effect

6.10 Antimony and Bismuth Compounds

References

Chapter 7: Sulfur, Selenium, and Tellurium Compounds

7.1 Sulfur Compounds

7.2 Synthesis of Organosulfur Compounds

7.3 Reactions of Organosulfur Compounds

7.4 Structure and Reaction of Hypervalent Organosulfur Compounds

7.5 Selenium and Tellurium Compounds

References

Chapter 8: Organohalogen Compounds: Fluorine and Iodine Compounds

8.1 Synthesis of Chlorine and Bromine Compounds

8.2 Fluorine Compounds

8.3 Iodine Compounds

References

Chapter 9: Atrane and Transannular Interaction: Formation of Hypervalent Bond

9.1 Introduction

9.2 Silatrane and Atrane

9.3 Transannular Interaction (1)

9.4 Transannular Interaction (2)

References

Chapter 10: Unsaturated Compounds of Main Group Elements of Third Period and Heavier

10.1 Introduction

10.2 Unsaturated Bonds of Group 15 Elements of Third Period and Heavier

10.3 Unsaturated Bonds of Group 14 Elements of Third Period and Heavier

10.4 Aromatic Compounds of Group 14 Elements

References

Chapter 11: Ligand Coupling Reaction

11.1 Introduction

11.2 Selectivity of Ligand Coupling Reaction: Theoretical Investigation

11.3 Ligand Coupling Reaction of Organic Compounds of Phosphorus, Antimony, and Bismuth

11.4 Ligand Coupling Reaction of Organic Compounds of Sulfur, Selenium, and Tellurium

11.5 Ligand Coupling Reaction of Organoiodine Compounds

References

Chapter 12: Hypervalent Carbon Compounds: Can Hexavalent Carbon Exist?

12.1 Introduction

12.2 Attempts for Pentacoordinate Hypervalent Carbon Species

12.3 Synthesis of Pentacoordinate Hypervalent Carbon Species (10-C-5) and Bond Switching at Carbon and Boron

12.4 Attempts to Hexacoordinate Hypervalent Carbon Species (12-C-6)

References

Index

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Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

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Library of Congress Cataloging-in-Publication Data:

Akiba, Kin-ya, 1936-

Organo main group chemistry / Kin-ya Akiba.

p. cm.

ISBN 978-0-470-45033-8 (pbk.)

1. Organic compounds. 2. Organic compounds-Synthesis.

3. Carbon compounds. 4. Chemistry Organic. I. Title.

QD251.3.A35 2011

547–dc22

2010050401

Preface

The fundamental and essential element of organic compounds is, without a doubt, carbon. There are excellent textbooks on organic chemistry, such as those written by McMurry, Jones, Jr., Morrison and Boyd, and Vollhardt and Schore. These are referred in undergraduate courses internationally and are available in almost all bookstores dealing with science. On the other hand, main group element chemistry has been traditionally described in inorganic chemistry textbooks before transition metal chemistry (such as in Cotton and Wilkinson, Huheey, Housecroft and Sharpe, and Schriver, Atkins and Langford).

Heteroatoms, that is, elements of groups 15, 16, and 17 bearing unshared electron pair (s) and elements of groups 1, 2, and 12–18 in which valence electrons reside in sp orbitals, are important elements contained in carbon skeletons; they modify the character of carbon compounds. The chemistry of the sp elements, namely, main group elements, has been investigated primarily to discover and to use their unique characteristics, as compared to carbon.

There are books and reviews on the chemistry of each main group element dealing with detailed and advanced researches. However, there is no concise book on organic chemistry focusing on the synthesis, structure, and reaction of main group element compounds.

This book, Organo Main Group Chemistry, consists of 12 chapters and 10 notes. Chapters 1–8 describe the fundamental and basic organic chemistry of main group elements that are classified according to their groups. These are appropriate for use as a textbook. Chapters 9–12 note the recent advances in the related field of hypervalent (higher coordinate) and hypovalent (lower coordinate) compounds of main group elements. The notes supplement the chapters by explaining basic ideas and also describing recent research in related fields.

Chapter 1 describes the fundamental properties of main group elements and explains the difference between a heteroatom and a main group element. Notes 1–3 remind readers of basic ideas of chemistry, emphasizing the importance of formal logic. Chapter 2 describes precisely the main group element effect in contrast to the heteroatom effect. Also, the effect of hypervalent bond, which does not appear in heteroatoms of a second period, is explained in considerable detail. Note 4 is a refresher on Hueckel molecular orbital (HMO) and electrocyclic reaction.

Chapters 3–8 discuss the synthesis, structure, and reaction of main group element compounds. Chapter 3 deals with groups 1 and 2, namely, lithium, magnesium, and copper compounds. Chapter 4 describes boron and aluminum compounds, and Chapter 5 explains silicon, tin, and lead compounds.

Chapter 6 describes compounds of group 15 elements of phosphorus, antimony, and bismuth. The synthesis of optically active phosphines, reaction of ylides, formation of phosphoranes, and effect of freezing pseudorotation are explained using phosphorus as a representative element. These are essentially common for compounds of groups 14, 15, 16, and 17, and the chemistry has been developed on phosphorus before that of sulfur because of its importance, and also for stability in handling the compounds. Note 6 mentions historical aspects of researches on hypervalent compounds, which stemmed from the dreams of Staudinger and Wittig. Note 7 explains possible mechanisms on nucleophilic substitution of MX4-type compounds.

Chapter 7 describes compounds of group 16 elements of sulfur, selenium, and tellurium. Note 8 explains the mechanism and dynamic aspects of edge inversion. Chapter 8 deals with halogen compounds, with emphasis on fluorine and iodine compounds because organochlorine and bromine compounds are quite common and are treated well in textbooks for undergraduates.

Chapters 9, 10, and 11 describe recent advances in researches on main group elements of third period and heavier ones. Chapter 9 deals with the formation of hypervalent (higher coordinate) bonds, including silatrane and atrane. Chapter 10 explains the synthesis of hypovalent (lower coordinate) compounds of groups 14, 15, and also that of aromatic compounds. Chapter 11 illustrates ligand coupling reaction (LCR) on compounds of groups 15, 16, and iodine. Note 9 illustrates the synthesis of hexavalent tellurium compounds and that of a cation and an anion of pentacoordinate tellurium bearing the same kind of ligand.

Chapter 12 describes the synthesis of hypervalent carbon compounds, namely, pentacoordinate hypervalent carbon species (10-C-5), and attempts to hexacoordinate (hypervalent) carbon species (12-C-6), supported by theoretical calculations. Note 10 illustrates the synthesis of main group element porphyrins of Sb and P in which central atoms are hypervalent.

References throughout this book are based on arbitrary choices by the author, and not at all comprehensive. Particularly, the references in Chapters 1–8, except in Chapter 2, contain basic and fundamental references on the fields, accompanied by newer ones, where appropriate. Most consist of references that the author has read carefully before and found to contain basic experimental results. They were used in lectures for undergraduate and graduate courses in Japanese universities. Chapters 9–12 deal with recent advances in the related fields; therefore, references are cited to show basic ideas and recent researches. References for notes were chosen based on the same standpoint as for the chapters. Advanced series, such as “Comprehensives” of organic synthesis, organometallic, and heterocyclic chemistry and the “Patai's series” on functional groups were not cited as references.

In Japanese bookstores dealing with sciences, we find a variety of textbooks originally written in English that had been translated into Japanese. For instance, seven textbooks mentioned at the beginning of this preface, except the one by Housecroft and Sharpe, had been translated and are being used in Japanese universities.

There are similar books and countless review articles on specialized topics originally written in Japanese. The Chemical Society of Japan has been editing the Encyclopedia of Experimental Chemistry (Jikken Kagaku Kouza). The recent fifth edition consists of 30 volumes; it includes all fields of chemical sciences.

However, the articles written in Japanese can neither be referred in original research papers of international journals, nor in books written in English. It is a great pity, but it is the reality. This book was originally written in Japanese and published by Kodansha Scientific, Inc., in Tokyo under the title Yuuki Tenkei Genso Kagaku (translated into English as Organo Main Group Chemistry) in 2008. I am grateful to Kodansha Scientific, Inc., for allowing me to use all the equations and schemes in the Japanese edition, without any restriction, to write the present revised English version.

I am thankful to the international reviewers nominated by John Wiley & Sons, who heartily recommended to publish this book in English. Also, I wish to acknowledge the patience and support of my family, and the kind cooperation, skill, and good cheer of the editors at Wiley.

Kin-ya Akiba

Professor Emeritus of Hiroshima University

Tokyo, Japan

November 2010