ORGANO MAIN GROUP CHEMISTRY

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1 ORGANO MAIN GROUP CHEMISTRY

2 ORGANO MAIN GROUP CHEMISTRY KIN-YA AKIBA A JOHN WILEY & SONS, INC., PUBLICATION

3 Copyright 2011 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) , fax (978) , or on the web at Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) , fax (201) , or online at Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) , outside the United States at (317) or fax (317) Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at Library of Congress Cataloging-in-Publication Data: Akiba, Kin-ya, 1936 Organo main group chemistry / Kin-ya Akiba. p. cm. ISBN (pbk.) 1. Organic compounds. 2. Organic compounds Synthesis. 3. Carbon compounds. 4. Chemistry Organic. I. Title. QD251.3.A dc Printed in Singapore obook ISBN: epdf ISBN: epub ISBN:

4 CONTENTS Preface ix 1 Main Group Elements and Heteroatoms: Scope and Characteristics Aufbau Principle and Sign of Orbitals / Electronic Configuration of an Atom: Main Group Elements and Heteroatoms / Fundamental Properties of Main Group Elements / Acidity of Carboxylic Acid and Substituent Effect / Heteroatom Effect / Stabilization of α-carbocation by Resonance: Stereoelectronic Effect / Coordination with Lewis Acids / 15 References / 16 Notes 1: Electronegativity 17 Notes 2: Notes 3: Importance of Formal Logic-I: Oxidation Number and Formal Charge 19 Importance of Formal Logic-II: Octet Rule, Eighteen-Electron Rule, Hypervalence 23 v

5 vi CONTENTS 2 Main Group Element Effect What Is Main Group Element Effect? / Single Bond Energy and π Bond Energy / Hypervalent Compound / Effect of Hypervalent Bond (1): 3c 4e Bond and Structure / Effect of Hypervalent Bond (2): Apicophilicity and Pseudorotation / Effect of Hypervalent Bond (3): Ligand Coupling Reaction (LCR) and Edge Inversion / Effect of σ X C / Effect of σx C /48 Notes 4: (σ, σ )and(π, π ): HMO (Hueckel Molecular Orbital) and Electrocyclic Reaction 57 3 Lithium, Magnesium, and Copper Compounds Synthesis / Structure / Reaction / Deprotonation as Base / Nucleophilic Reaction / Conjugate Addition of Lithium Dimethylcuprate / 76 References / 77 4 Boron and Aluminum Compounds Synthesis / Structure / Reaction / 84 References / 88 5 Silicon, Tin, and Lead Compounds Synthesis / Reaction / Organotin and Lead Compounds / 100 References / 104 Notes 5: Stable Carbene and Its Complex Phosphorus, Antimony, and Bismuth Compounds Phosphorus Compounds / Synthesis of Organophosphorus Compounds / 113

6 CONTENTS vii 6.3 Tertiary Phosphine and Its Nucleophilic Reaction / Arbuzov Reaction / Perkow Reaction / Synthesis of Optically Active Phosphines / Ylide and Wittig Reaction and Related Ones / Reactions of Phosphonium Salts and Formation of Phosphoranes / Freezing BPR and Its Effect / Antimony and Bismuth Compounds / 143 References / 146 Notes 6: Dreams of Staudinger and Wittig 149 Notes 7: Stereochemistry in Nucleophilic Substitution of MX 4 -type Compounds: Inversion or Retention Sulfur, Selenium, and Tellurium Compounds Sulfur Compounds / Synthesis of Organosulfur Compounds / Reactions of Organosulfur Compounds / Structure and Reaction of Hypervalent Organosulfur Compounds / Selenium and Tellurium Compounds / 175 References / 178 Notes 8: Inversion Mechanism of NH 3 and NF 3 :Vertex Inversion or Edge Inversion Organohalogen Compounds: Fluorine and Iodine Compounds Synthesis of Chlorine and Bromine Compounds / Fluorine Compounds / Iodine Compounds / 195 References / Atrane and Transannular Interaction: Formation of Hypervalent Bond Introduction / Silatrane and Atrane / Transannular Interaction (1) / Transannular Interaction (2) / 210 References / 211

7 viii CONTENTS 10 Unsaturated Compounds of Main Group Elements of Third Period and Heavier Introduction / Unsaturated Bonds of Group 15 Elements of Third Period and Heavier / Unsaturated Bonds of Group 14 Elements of Third Period and Heavier / Aromatic Compounds of Group 14 Elements / 222 References / Ligand Coupling Reaction Introduction / Selectivity of Ligand Coupling Reaction: Theoretical Investigation / Ligand Coupling Reaction of Organic Compounds of Phosphorus, Antimony, and Bismuth / Ligand Coupling Reaction of Organic Compounds of Sulfur, Selenium, and Tellurium / Ligand Coupling Reaction of Organoiodine Compounds / 241 References / 245 Notes 9: Hexavalent Organotellurium Compounds Hypervalent Carbon Compounds: Can Hexavalent Carbon Exist? Introduction / Attempts for Pentacoordinate Hypervalent Carbon Species / Synthesis of Pentacoordinate Hypervalent Carbon Species (10-C-5) and Bond Switching at Carbon and Boron / Attempts to Hexacoordinate Hypervalent Carbon Species (12-C-6) / 259 References / 262 Notes 10: Main Group Element Porphyrins 265 Index 269

8 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 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. ix

9 x PREFACE 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 MX 4 -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

10 PREFACE xi 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 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. Professor Emeritus of Hiroshima University Tokyo, Japan November 2010 Kin-ya Akiba

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