Organometallics in Synthesis A Manual 2 ed reprint

2002 2nd Edition Schlosser Manfred. (Ed.) new

release 2025

Order now at ebookgate.com

( 4.5/5.0 ★ | 338 downloads )

https://ebookgate.com/product/organometallics-in-synthesis-a-
manual-2-ed-reprint-2002-2nd-edition-schlosser-manfred-ed/
Organometallics in Synthesis A Manual 2 ed reprint 2002 2nd
Edition Schlosser Manfred. (Ed.)

EBOOK

Available Formats

■ PDF eBook Study Guide Ebook

EXCLUSIVE 2025 ACADEMIC EDITION – LIMITED RELEASE

Available Instantly Access Library

Instant digital products (PDF, ePub, MOBI) available
Download now and explore formats that suit you...

Organometallics in Synthesis Third Manual 3 ed 3rd Edition

Schlosser Manfred. (Ed.)

https://ebookgate.com/product/organometallics-in-synthesis-third-
manual-3-ed-3rd-edition-schlosser-manfred-ed/

ebookgate.com

Introduction to Graph Theory 2, 2002 reprint Edition

Douglas B. West

https://ebookgate.com/product/introduction-to-graph-
theory-2-2002-reprint-edition-douglas-b-west/

ebookgate.com

Russia A History 1997 2nd ed 2002 2nd ed. 2002 Edition

Gregory L. Freeze

https://ebookgate.com/product/russia-a-history-1997-2nd-ed-2002-2nd-
ed-2002-edition-gregory-l-freeze/

ebookgate.com

Medieval Russian Culture Vol 2 2nd. rev. ed. Reprint 2020

Edition

https://ebookgate.com/product/medieval-russian-culture-vol-2-2nd-rev-
ed-reprint-2020-edition/

ebookgate.com
Physics of Semiconductors 2002 Proceedings of the 26th
International Conference Edinburgh 29 July to 2 August
2002 1st Edition J.H Davies (Editor)
https://ebookgate.com/product/physics-of-
semiconductors-2002-proceedings-of-the-26th-international-conference-
edinburgh-29-july-to-2-august-2002-1st-edition-j-h-davies-editor/
ebookgate.com

Synthesis of Polymers New Structures and Methods in 2 Vol

1st Edition Schlüter A. Dieter. (Ed.)

https://ebookgate.com/product/synthesis-of-polymers-new-structures-
and-methods-in-2-vol-1st-edition-schluter-a-dieter-ed/

ebookgate.com

Diasporas 2. reprint Edition Dufoix

https://ebookgate.com/product/diasporas-2-reprint-edition-dufoix/

ebookgate.com

Globalization A Very Short Introduction 2nd Edition

Manfred Steger

https://ebookgate.com/product/globalization-a-very-short-
introduction-2nd-edition-manfred-steger/

ebookgate.com

Handbook of Metathesis Volume 2 Applications in Organic

Synthesis 2nd Edition Robert H. Grubbs

https://ebookgate.com/product/handbook-of-metathesis-
volume-2-applications-in-organic-synthesis-2nd-edition-robert-h-
grubbs/
ebookgate.com
Manfred Schlosser

Li Be B
Na Mg Al Si

K Ti V Cr Mn Fe Ni Cu Zn
Zr Pd Sn
Cs Ba
Copyright © 2002 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,
West Sussex PO19 8SQ, England

Telephone (C44) 1243 779777

First printed in paperback with corrections February 2004

Email (for orders and customer service enquiries): [email protected]
Visit our Home Page on www.wileyeurope.com or www.wiley.com

All Rights Reserved. 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 under the terms of
the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency
Ltd, 90 Tottenham Court Road, London W1T 4LP, UK, without the permission in writing of the Publisher. Requests to
the Publisher should be addressed to the Permissions Department, John Wiley & Sons Ltd, The Atrium, Southern Gate,
Chichester, West Sussex PO19 8SQ, England, or emailed to [email protected], or faxed to (C44) 1243 770620.

This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It
is sold on the understanding that the Publisher is not engaged in rendering professional services. If professional advice
or other expert assistance is required, the services of a competent professional should be sought.

Other Wiley Editorial Offices

John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA

Jossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USA

Wiley-VCH Verlag GmbH, Boschstr. 12, D-69469 Weinheim, Germany

John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia

John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02-01, Jin Xing Distripark, Singapore 129809

John Wiley & Sons Canada Ltd, 22 Worcester Road, Etobicoke, Ontario, Canada M9W 1L1

Wiley also publishes its books in a variety of electronic formats. Some content that appears
in print may not be available in electronic books.

Library of Congress Cataloging-in-Publication Data

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN 0 471 98416 7 (cased)

ISBN 0 470 84159 1 (paperback)

Typeset in 10/12pt Times by Laserwords Private Limited, Chennai, India

Printed and bound in Great Britain by Biddles Ltd, King’s Lynn
This book is printed on acid-free paper responsibly manufactured from sustainable forestry
in which at least two trees are planted for each one used for paper production.
List of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Preface to the First Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

Preface to the Second Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

I Organoalkali Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Manfred Schlosser

II Organotin Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353

James A. Marshall

III Organoboron Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465

Keith Smith

IV Organoaluminum Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

Hisashi Yamamoto

V Organozinc Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579

Eiichi Nakamura

VI Organocopper Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665

Bruce H. Lipshutz
vi

VII Organotitanium Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817

Manfred T. Reetz

VIII Organozirconium Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 925

Ei-ichi Negishi

IX Organoiron and Organochromium Chemistry . . . . . . . . . . . . . . . . . 1003

Martin F. Semmelhack

X Organopalladium Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123

Louis S. Hegedus

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1219
LOUIS S. HEGEDUS Colorado State University, Fort Collins, Colorado, USA

BRUCE H. LIPSHUTZ Department of Chemistry, University of California, Santa

Barbara, California, USA

JAMES A. MARSHALL Department of Chemistry, University of Virginia,

Charlottesville, Virginia, USA

EIICHI NAKAMURA Department of Chemistry, The University of Tokyo, Tokyo,

Japan

EI-ICHI NEGISHI Department of Chemistry, Purdue University, West

Lafayette, Indiana, USA

MANFRED T. REETZ Max-Planck-Institut für Kohlenforschung, Mülheim/Ruhrt,

Germany

MANFRED SCHLOSSER Institut de Chimie moléculaire et biologique, Ecole

Polytechnique Fédérale de Lausanne Switzerland

MARTIN F. SEMMELHACK Department of Chemistry, Princeton University, Princeton,

USA

KEITH SMITH Department of Chemistry, University of Wales, Swansea, UK

HISASHI YAMAMOTO Department of Chemistry, The University of Chicago, USA

The origin of this Manual, was a series of three post-graduate workshops which I had the
privilege to host in the late eighties. These five-day seminars provided ample opportunity
for the participants to talk to the lecturers, solve exercises and, in 1987 at least, to
practise their new skills in the laboratory. One common feature became apparent in all
such interactions between tutors and novices: the psychological and practical barrier for
newcomers to enter the field of organometallic chemistry is still very high.
Therefore, this Manual is meant primarily for those researchers who have not yet had a
chance to familiarize themselves with the basic concepts and techniques of organometallic
reactions. It is a nuts-and-bolts text: full of useful hints, rules of thumb and, last but not
least, carefully selected working procedures. Thus, it summarizes what organometallic
reagents can do for modern organic synthesis and at the same time explains how they are
conveniently employed.
However, as Ludwig Boltzmann recognized, ‘nothing is more practical than a good
theory’. The message applied to our case is that sound mechanistic insight is required if
we wish not only to document the course of known reactions but also predict the outcome
of future experiments. Therefore, despite its down-to-earth approach, this Manual puts
great emphasis on the presentation of first principles that can provide a rational basis for
understanding organometallic reactivity, a fascinating and at the same time still widely
mysterious subject.
In order not to discourage the reader by too voluminous a book, we had to restrict the
coverage to a selection of the most popular metals and methods. Hence, many important
reagents and topics had to be neglected for the moment. They may, however, be included
in a future, more comprehensive edition.
x

It is now my pleasure to express by profound gratitude to my co-authors who, notwith-

standing their numerous other commitments, have agreed to share their expertise with
the reader and thus to contribute to the propagation of organometallics in synthesis. I
wish also to acknowledge the help of my coworkers who have checked many working
procedures. Finally, I am indebted to my wife Elsbeth, who has made the Chem-Art china
ink drawings (contributions Nos 1, 2, 3 and 8) with artistic skill and aesthetic taste.

Lausanne, Spring 1994 Manfred Schlosser

Compared with the first edition of the Manual, the second has almost doubled in size.
Thus, this monograph on organometallics is far from just a remake or update of a
successful earlier version but, as the Publisher notes, is essentially a new book. Four
additional chapters have been included featuring the chemistry of tin, zinc, zirconium,
and chromium and iron. Such an extension of useful organometallic procedures reflects
the continuing evolution of organic synthesis, which increasingly relies on a greater
percentage of the Periodic Table. Previous chapters have been extensively reworked and
updated. For example, the number of Tables to be found in the chapter covering alkali
and alkali-earth derived reagents has increased from 12 to 166.
Nonetheless, maintained throughout is the original, underlying concept behind creation
of the Manual. That is, it strives to offer guidance in the form of countless “cookbook
recipes,” along with recommendations on associated equipment needs as well as practical
advice at critical stages. At the same time, indispensable mechanistic insight is provided
which is crucial to those who wish to apply these existing tools rationally and to contribute
to the further development of novel reagents and methodology.
Although not always easy, the role of the coordinating Editor can be quite rewarding.
I have enjoyed and appreciated the numerous comments and suggestions colleagues and
reviewers have shared with me. A good deal of the recent accomplishments have to be
credited to them. To name at least one person, I wish to mention the invaluable input
made by my friend Bruce Lipshutz who was always available when help or advice was
sought.

Lausanne, Summer 2001 Manfred Schlosser

I
Organoalkali Chemistry
MANFRED SCHLOSSER
Section de Chimie (BCh), Université, CH-1015 Lausanne, Switzerland

Li Be
Na Mg
K Zn

Cs Ba

Organometallics in Synthesis: A Manual. Edited by Manfred Schlosser.

© 2002 John Wiley & Sons Ltd
2 Hints and Road Maps

Hints and Road Maps

Nomenclature and Formulas
It was not intended to apply systematic IUPAC rules strictly and at all events. On the
other hand, we feel the time has come to abolish some anachronisms. The Old-German
‘n-alkyl’ having never been part of an authorized nomenclature, should be definitively
abrogated and LiCH2 CH2 CH2 CH3 be unequivocally named butyllithium.
The formula drawings shown try to reflect the structure of the various organometallic
species as faithfully as possible. There is one major exception. For easy comparison with
their precursors, N-deprotonated carboxamides and carbamates (see, e.g., Tables 121 and
124) are frequently represented as lithium N-acylamides rather than O-lithio azaenolates,
as the true position of the metallomeric equilibrium would suggest:
M M
N C O N C O
R R
Coverage of this Chapter
This Chapter deals with all kinds of organometallic species containing a carbon–alkali
or a carbon–alkaline earth bond. However, weakly basic species (pKa  30) such as
acetylides, cyclopentadienides, indenides, fluorenides and d-orbital resonance stabilized
compounds (such as ˛-metalated dithioacetals) are only marginally treated, if at all.
Enolates and N-deprotonated pyrroles, indoles etc. or ˛-deprotonated Schiff bases and
picolines, sulfones and phosphonates as any other derivative carrying the metal at a hetero
rather than a carbon atom are almost totally omitted from the present review.

Generation of Organometallic Species: Ordering Principles and Tables

The most voluminous part of this Chapter is Section 4, which summarizes the various
methods available for the generation of reactive organometallic intermediates. The
contents within each subcategory always follow in the same order: we start with sp3 -
centers, first considering saturated aliphatic structures before turning to unsaturated ones
stabilized by allylic, propargylic or benzylic resonance, and terminate with sp2 -centers,
first examining 2-alkenylmetals and ferrocenylmetals before continuing with arylmetals
and finally ending with five- and six-membered metalated heterocycles. If substituents
are present, the one maintaining the closest proximity to the metal-bearing center has the
priority. In the case of equal distances, nitrogen functions preceed oxygen functions and
the latter halogen atoms or groups.
All three ‘navigational charts’ displayed on the opposite page refer to Section 4. Table 1
summarizes the principal options available for the preparation of organometallic species.
Table 2 surveys over the 52 Tables that exemplify the metalation of saturated or unsat-
urated, unsubstituted or heterosubstituted acyclic hydrocarbons, of metallocenes and of
arenes. Table 3 covers the 13 Tables, in which typical metalation reactions of 5- or 6-
membered heterocycles are compiled.
Manfred Schlosser : Organoalkali Chemistry 3

Graphical Guideposts to Section I/4

Table 1. Principal Methods of MR Generation

With elemental metal (M): Electrofugal With organomet. reagent:
reductive insertion group permutat. interconversion

CC
C pp. 86 – 101 X (halogen) pp. 101 – 137 
CC
C

CC pp. 138 – 148 Y (chalcogen) pp. 148 – 155 
C

CC pp. 155 – 159 Q (metalloid) pp. 159 – 171 
CC
Table 3. Metalation of

C pp. 171 – 177 C (carbon) pp. 177 – 181 
C five- and six-
membered heterocycles

C pp. 181 – 185 H (hydrogen) pp. 185 – 284 
CC
C

M Table 132
N (p. 236)
R
Table 2. Metalation of hydrocarbons and metallocenes Table 133
M
N (p. 237)
NR2 F
R
H N(M)R OR Cl
M N Table 134
XD R Br N (p. 238)
C NR2 R
SiR3 C OM I M N
Table 135
C N(M)R CF3 N (p. 239)
R
Tables Tables Table 136
M C X Table 80 Table 90 M
81 – 86 87 – 89 O (p. 240)
(p. 186) (p. 196)
(pp. 187 – 192) (pp. 93 – 195)
Table 137
Tables Tables M
M C C C Table 100 Table 103 S (p. 241)
91 – 99 101 – 102
X (p. 205) (p. 207)
(pp. 187 – 192) (pp. 206 – 207)
M Table 138
X N (p. 242)
Tables O
Table 104 Table 105 Table 108
106 – 107
M C (p. 208) (p. 209) (p. 212)
(pp. 210 – 211) M N Table 139
O (p. 243)
X Tables Tables Tables
Table 109
M C C 110 – 113 114 – 115 116 and 117
(p. 213) M Table 140
(pp. 214 – 217) (pp. 218 – 219) (pp. 220 – 221) N
S (p. 243)
X
Table 118 Table 118 — — M N Table 244
M
(p. 222) (p. 222) (p. 243)
M″ S

X Tables Tables Tables Tables

Table 119 M
M 120 – 124 125 – 128 129 – 131 142 – 144
(p. 223) N
(pp. 224 – 228) (pp. 229 – 232) (pp. 233 – 235) (p. 245 – 247)
4 Hints and Road Maps

Contents
1 Background 5
1.1 Glimpses on History 5
1.2 The Organometallic Approach to Synthesis 7
1.3 Metal Tuning 10

2 Structure and Mobility 10

2.1 The Nature of the Organometallic Bond 11
2.2 Aggregation and Coordination 12
2.3 Stereomutations and Stereopreferences 26

3 Reactivity and Selectivity 45

3.1 The Chemical Potential of Organometallic Reagents 46
3.2 Metal Effects on Basicities and Reactivities 50
3.3 Organometallic Reaction Mechanisms 68

4 Generation of Polar Organometallic Intermediates 85

4.1 Displacement of Halogens 86
4.2 Displacement of Chalcogens 137
4.3 Displacement of Metalloids 155
4.4 Displacement of Carbon 171
4.5 Displacement of Hydrogen 181

5 Handling Polar Organometallic Compounds 284

5.1 Hazards 284
5.2 Equipment 285
5.3 Commercial Reagents 288
5.4 Storability of Reagents 289
5.5 Analysis 293

6 References 297
Manfred Schlosser : Organoalkali Chemistry 5

1 Background

All chapters in this book focus on reactions and reagents. However, in order to
understand what drives organometallic reactivity, we have to know about structures and
mechanisms. Moreover, a look back shows us how things started and how much effort,
combined with imagination, was needed to achieve the position organometallic methods
nowadays occupy in organic synthesis.

1.1 Glimpses on History

The cradle of polar organometallic chemistry stood some 150 years ago in Northern
Hesse[1 – 3] . There, in 1831, Friedrich Wöhler became a teacher at the newly founded
Higher Industrial School (Höhere Gewerbeschule) in Cassel. Previously, he had held an
appointment at a similar institution in Berlin where he had succeeded in the preparation of
the ‘natural product’ urea from the indisputably inorganic precursors ammonia and silver
or lead cyanate[4,5] . Thus, he had defeated the dogma of the indispensable vis vitalis and
had fired the starting shot in the race towards organic synthesis. An outburst of cholera
prompted him to leave the Prussian capital and to return to the proximity of his native
town. Among his numerous noteworthy accomplishments in Cassel was the preparation
of diethyltellurium[6] as the first main group organometallic compound. This discovery,
however, remained without aftermath.
In 1836, Wöhler occupied the vacant chair of chemistry at the university of Göttingen
while the young Privatdozent Robert Wilhelm Bunsen, became his successor in Cassel.
Scientifically ambitious, Bunsen decided to tackle one of the greatest experimental chal-
lenges of his time. He was determined to solve the mysteries of the dreadful Cadet’s
liquor, an atrociously smelling, poisonous distillate that forms when arsenic and potas-
sium acetate are exposed to red heat. At the risk of his health, he managed to isolate the
main component and to identify its elementary composition as C4 H12 As2 O[7] . Although
he initially called the new substance alcarsine oxyde, he soon adopted the more revealing
name of cacodyl oxyde (˛óς D stinking, óυς D odor).
Nowadays, we can unambiguously assign the structure of bis(dimethylarsanyl) oxide
to this compound. However, in the middle of last century, the notions of chemical
bonding, valency and connectivity had not yet become established, although a forerunner
concept had just emerged. The great Swedish chemist Jons Jacob Berzelius, a dominant
authority of the time, conceived organic molecules to consist of two electrostatically
matched parts, for example ether of ethyl and oxide subunits, exactly as mineral salts
are made up from cations and anions. If the organic world really were nothing but a
reproduction of the inorganic, should one not be able to identify highly reactive molec-
ular fragments in just the same way as metallic sodium and elementary chlorine had been
obtained from sodium chloride? Indeed, there was a general consensus that the isolation of
6 I/1 Background

organic radicals in the free state would constitute compelling evidence for the correctness
of Berzelius’ electrostatic concepts which postulated a dualistic constitution of all matter
and which was, at the beginning at least, cognate with the ‘radical theory’ promoted by
Dumas, Liebig and Wöhler. However, all experiments undertaken in this respect so far,
had failed.
Bunsen was the man to create the sensation. He treated cacodyl oxyde with concentrated
hydrochloric acid to obtain cacodyl chloride (dimethylarsanyl chloride). This substance
was painstakingly purified and filled into glass ampoules which contained activated zinc
sheets and which had previously been purged with carbon dioxide before they were flame
sealed and heated on a water bath. After three hours, the vessel was opened, the zinc
chloride formed extracted and the remaining oil collected. When exposed to air, the
compound spontaneously ignited. It was, as we now know, tetramethyldiarsane. Bunsen,
however, believed he had isolated the free cacodyl radical, and many of his contemporaries
shared this conviction.

H3C CH3 HCl H3C Zn H3C H3C CH3

As O As As Cl As• As As
H3C CH3 H3C H3C H3C CH3

Otherwise feared as a merciless critic, Berzelius wholeheartedly praised Bunsen. The

latter moved as an associate (1839) and later as a full professor (1841) to Marburg before,
after a short interlude in Breslau, he ascended in 1852 to the then most prestigious position,
the chemistry chair in Heidelberg. His rising renown attracted scholars from all over the
world. One of them, Edward Frankland, hoped to obtain the free ethyl radical by applying
his mentor’s method, i.e., the reduction of a halide with zinc, to ethyl iodide. He prepared
the first organozinc compound instead[8] . A few years later, John A. Wanklyn, another
English research fellow in Bunsen’s laboratory, treated dialkylzincs with sodium and thus
produced the first, though ill-defined, organosodium species (which actually combined
with unconsumed precursor material to afford a sodium triethylzincate complex[9] ).

Zn
H5C2 I H5C2 ZnI (H5C2)2 Zn

Na
(H5C2)2Zn H5C2 Na (H5C2)3Zn Na

The work of Wanklyn was followed up by Paul Schorigin (from 1906) and Wilhelm
Schlenk (from 1922), while Frankland inspired Sergei Nikolaijevitch Reformatzky (from
1887), whose ˛-bromo ester-derived zinc enolates became the first synthetically useful
organometallic reagents. Philippe Barbier (from 1899) and Victor Grignard (from 1900)
switched from organozinc to organomagnesium compounds. The latter, being univer-
sally accessible and at the same time more reactive, soon became favorite tools for
Manfred Schlosser : Organoalkali Chemistry 7

preparative chemistry. However, it still needed the ingenuity and perseverance of pioneers
such as Morris S. Kharasch, Avery A. Morton, Henry Gilman, Georg Wittig and Karl
Ziegler, who systematically developed, complemented and refined the methods that have
become the foundations of the organometallic approach to synthesis. The seeds planted
by such outstanding researchers in the 1930s and 1940s began to grow in the years
after the second World War. Within a few decades, organic synthesis had undergone a
complete metamorphosis and polar organometallic chemistry had played a crucial role in
this evolutionary process (Fig. 1).

1840
Bunsen
1850
Frankland
1860
Wanklyn

1870

1880

1890 Reformatzky

1900 Grignard

1910 Schorigin

1920 Schlenk

1930 Morton Gilman Wittig Kharasch Ziegler

1940

Figure 1. Genealogy of polar organometallic chemistry.

1.2 The Organometallic Approach to Synthesis

What is so special and novel about the organometallic approach to organic synthesis?
To gain this perspective, first consider the most classical and typical organic reac-
tion, the SN 2 process (route a2 , in the scheme overleaf): a standard nucleophile M–Nu
(iodide, cyanide, enolate, etc.) encounters in a bimolecular collision a carboelectrophile
C X (mostly derived from the corresponding hydrocarbon; route a1 ) and, attacking
from the rear, promotes the replacement of the nucleofugal leaving group X (halide,
sulfonate, etc.) under a Walden inversion of configuration. In general, such nucleophilic
substitution proceeds with great ease if the carboelectrophilic substrate has a methyl
or primary alkyl group as the organic entity. With a secondary alkyl carbon as the
8 I/1 Background

reaction center, generally only a poor yield is obtained. Worse, tertiary alkyl, 1-alkenyl,
1-alkynyl, aryl, hetaryl and cyclopropyl halides or sulfonates are completely SN 2 inactive.
In other words, the concerted bimolecular nucleophilic substitution has a fairly narrow
scope of applicability.
Organometallic chemistry now offers a way out of this dilemma. Suppose we wish to
convert an aryl bromide into the corresponding benzoic acid. It would be more than naive
to treat it with potassium cyanide in the hope of obtaining in this way the aryl nitrile,
which subsequently could be hydrolyzed. However, when it is allowed to react with
magnesium or lithium (butyllithium may also be used advantageously, as we shall see
later), a highly reactive organometallic species is formed (route b) which can be readily
condensed with cyanogen bromide or cyanogen to give the expected nitrile (route c2 ).
Alternatively, the carboxylic acid may be directly obtained by nucleophilic addition of
the organometallic intermediate to carbon dioxide.
Switching from a halide to an organometallic compound implies an ‘Umpolung’, the
term being coined by G. Wittig[10] and the concept popularized by D. Seebach[11] . The
inversion of familiar product polarities gratifies the experimentalist with a second option:
he may now select his preferred building block from a fresh set of electrophiles El–X,
the choice again being embarrassingly large. It is like reshuffling a pack of cards and
starting the game over again.
M− Nu M−X
H − X′

X − X′ C X a2 C Nu

a1

2M
C H b
M−X
c1

M −R CM c2 C El
H− R

El− X M− X
The reductive or permutational replacement of halogen by a metal M (route b) can
hardly fail, and subsequent electrophilic replacement of the metal (route c2 ) rarely causes
trouble. However, the selective access to the required starting material (route a1 ) may
give us a true headache. In general, neither such a halide nor the corresponding alcohol
exists as such in nature. Ultimately, most have to be prepared from a suitable, saturated
or unsaturated hydrocarbon. The site-selective introduction of the heteroatom is far from
being a trivial task. There is a great temptation to try a shortcut and to convert the
hydrocarbon directly into an organometallic intermediate (route c1 ).
Manfred Schlosser : Organoalkali Chemistry 9

This is easier said than done. Simple hydrocarbons are only minimally acidic and
hence extremely reluctant to undergo deprotonation. The second obstacle is that several
or even many different hydrogen atoms, not just one, are present in ordinary substrates
(omitting the few high-symmetry structures known, such as benzene, neopentane and
cyclohexane). We have to learn how to exploit subtle differences in their environment
in order to discriminate between them chemically. This means that we have to conceive
metalating reagents that unite two seemingly incompatible reactivity profiles: maximum
reactivity and maximum selectivity. A substantial part of this Chapter is devoted to this
fascinating problem. It will be shown how the two antagonistic features can be reconciled
and what impressive practical results can be achieved in this way.
In summary, this Chapter assigns the highest priority to the generation of organometal-
lic reagents, although their transformation, their reactivity or other properties will not be
completely neglected. When we consider the various possibilities that exist for the prepa-
ration of key organometallic intermediates, emphasis is put on the most direct method,
the permutational hydrogen/metal exchange.
This Chapter is restricted to the so-called polar organometallics [12] (Fig. 2). This class
of compounds includes the derivatives of the most common alkali and alkaline earth
metals and extends into the area of the organozinc compounds. However, the latter
reagents deserve to be treated in a separate review (see Chapter V).

Li
Na Mg

K Ca

Cs Ba

Figure 2. A periodic table featuring the major elements used as constituents of ‘polar’ organometallic
reagents.

Although all these species are characterized by a polar carbon–metal bond, the degree
and pattern of polarity vary significantly with the element. Whereas nucleophilicity and
basicity are the absolutely dominant features of organic derivatives of potassium, cesium
and barium, the reactions of lithium, magnesium and zinc compounds are, in increasing
order, triggered by the electrophilicity (Lewis acidity) of the metal. As will be stressed
over and over again, the individuality of the metal involved is the most critical parameter
for designing tailor-made organometallic reactions.
10 I/2 Structure and Mobility

1.3 Metal Tuning

The present contribution avoids dealing with organic derivatives of transition elements,
no matter whether produced in a stoichiometric reaction or as a transient species in
a catalytic cycle. However, one cannot ignore the interdependence or the complemen-
tarity of main group and transition block chemistry in modern organic synthesis. For
example, organotitanium and organocopper compounds are most conveniently prepared
through organolithium or organomagnesium reagents. Organocopper and organopalla-
dium compounds allow us to escape definitively from the SN 2 restrictions even in such
cases when, despite Umpolung, no suitable electrophile can be matched with a polar
organometallic reagent. The area of transition element chemistry (like that of boron,
aluminum and tin) is treated in the following Chapters by some of the most competent
workers in the field.

2 Structure and Mobility

A quarter of a century ago, the term ‘polar organometallics’[12] was coined as a common
designation for the organic derivatives of magnesium, zinc, lithium, sodium and potas-
sium. Although their first appearance was rather inconspicuous, they have subsequently
become key reagents for modern organic synthesis. At first sight they are all endowed with
the same high basicity and nucleophilicity. Such behavior is readily compatible with a
bond model in which the metal-bearing carbon carries a negative charge and the inorganic
counterpart is a cation. Therefore, such reactive intermediates have frequently been called
‘carbanions’[13,14] . This primitive description was very helpful when, in the years after
the Second World War, G. Wittig and other pioneers began to advertise the rapidly devel-
oping branch of organometallic chemistry. Nevertheless, the conceptual reduction of real
organometallic species to fictional carbanions is an oversimplification which must lead to
misjudgments. In fact, no difference in organometallic reactivity patterns can be rational-
ized unless the metal and its specific interactions with the accompanying carbon backbone,
the surrounding solvent, and the substrate of the reaction, are explicitly taken into account.
In other words, in order to understand reactivity we need a detailed knowledge of the
structures involved. Only if we have a realistic idea about the nature of an organometallic
bond can we dare to predict what changes it may undergo under the influence of a
suitable reaction partner until a thermodynamically more stable entity will emerge from
such a molecular reorganization. For this reason, this Chapter aims to provide a suitable
descriptions of the specific interactions that exist between metals and carbon, of the
unique architecture of polar organometallic compounds, and of fluxionalitities that are
characteristic of such species.
Manfred Schlosser : Organoalkali Chemistry 11

2.1 The Nature of the Organometallic Bond

Many of us may remember to have heard in highschool that metals want to get rid
of their valence electrons in order to become cations having the same electron shell as
noble gases. Although common, this belief is entirely wrong. We just have to look up
the ionization potentials of monoatomic metals in order to convince ourselves of the
contrary. Stripping off an electron from even the most ‘electropositive’ metals requires
energies of 124 (lithium), 118 (sodium), 100 (potassium), 98 (rubidium) and 90 (cesium)
kcal/mol[15] . Why should a metal want to become a cation at all? Actually it does not.
As do other elements, it merely seeks to share electrons with other atoms by forming a
chemical compound . However, in the case of metals this is not a trivial matter.
Let us consider a metal atom, say lithium, in the gas phase. When it is allowed to
combine with another radical, binding energy is produced. If a lithium chloride molecule
is formed, this gain amounts to 112 kcal/mol. In order to assess on this basis its heat
of formation from the elements, one has to deduct half of the dissociation energy of
elemental chlorine (58 kcal/mol) and, in addition, the heat of fusion, vaporization and
atomization of bulk lithium (altogether some 70 kcal/mol). In other words, the formation
of lithium chloride from the elements is an endothermic process as long as monomeric
species are generated in the gas phase. This conclusion holds also for other alkali metal
halides. They become thermodynamically strongly favored only in the solid state. What
structural features make the crystal lattice so advantageous?
The answer can be found in any textbook of general chemistry. Due to the dense
packing of the ball-like ions, each is surrounded by several, mostly six, counterions. In
this way the attraction between oppositely charged particles increases steeply, whereas
the repulsion of ions having the same sign remains moderate because of the longer inter-
nuclear distances. The electrostatic model can also be used to describe smaller molecular
packages such as aggregates or clusters. As an extension, solvation may be portrayed as
a charge–dipole interaction.
Although nothing is wrong with these ideas, we wish to adopt a different point of
view or, more properly, to use a different vocabulary. We prefer to conceive of the
forces holding together a sodium chloride crystal as ‘partial bonds’ (electron-deficient
bonds) rather than ‘ionic bonds’. This approach has the merit of universality; it creates a
continuum of binding interactions spanning from perfectly covalent to totally polar bonds
as the extremes.
The reader may immediately wish to object. How can somebody dare to deny the
ionic nature of the sodium chloride crystal? Has it not been proved that within the radii
of 0.95 and 1.81 Å around sodium and chloride nuclei precisely 10 and 18 electrons,
respectively, can be found and that, most revealingly, the electron density between such
spheres drops to zero[16 – 22] ? Yet electron population analyses may be fallicious[23 – 27] . A
lithium atom in the gas phase would have to be visualized as an ‘electride’ if treated in
the same way as solid lithium fluoride: at 0.65 Å from the nucleus the electron density
is zero; inside of this ‘ion radius’ confinement we find two 1s, but outside the entire 2s
valence electron[28,29] !
12 I/2 Structure and Mobility

To feel reassured, the reader should not forget how imperfect any description of the
physical reality is when man-made equations, images and semantics are used. Hence
the liberty, if not necessity, to choose in a given case the model which appears to be the
most appropriate, is required. For example, the  (‘banana bond’) and the  depiction
of ethylene are equivalent. Depending on the situation, one or the other representation
may be more suitable. In the same way, it is a matter of convenience whether to deal
with metal derivatives in terms of ionic and partial bonds. As all molecular ensembles
are tied together by the electrostatic attraction between protons and electrons, ultimately
both models must converge and lead to the same conclusions.
With all these precautions in mind, we now attempt to rationalize the most character-
istic features of metal binding, in particular aggregation and coordination. The selection
of examples is focused entirely on carbon–metal compounds, although metal amides,
metal alkoxides or aroxides and metal halides exhibit the same structural phenomena.

2.2 Aggregation and Coordination

Subunits can assemble to afford larger chemical entities when the attractive forces
overcompensate the repulsive forces. In order to minimize repulsion, electrons must be
able to spread out over a maximum of space. In order to maximize attraction, the electrons
have to approach the atomic nuclei as closely as possible. These seemingly contradictory
requirements can best be reconciled if the electrons surround the atomic nuclei spherically.
Within a diatomic molecule (1) such as lithium chloride, electrons will inevitably concen-
trate between the two poles of attraction, the metal and halogen nuclei, and thus create
an energetically unfavorable asymmetric charge distribution. As we have already seen, a
naked metal ion (2) is worse, being extremely energetic if kept in empty space. However,
in a crystal lattice (3) it is surrounded by four, six or eight heteroatomic neighbors which
enwrap it spherically and share valence electrons with the metal. The interaction between
a metal atom and solvent molecules (S ) in a solvate (4) can be treated in a similar
manner.
M X M

1 2
•
M
M M

δ
δ Sv X
X
Sv δ M M
M
δ X
Sv δ X
Sv

4 3
Manfred Schlosser : Organoalkali Chemistry 13

The typical coordination number of lithium[30] , magnesium[31] and zinc[32] is four, and
of larger cations such as sodium[33] or potassium[34] six. Special effects, in particular steric
hindrance, may deplete the coordination sphere and reduce it to two ligands [e.g. lithium
perchlorate dietherate (5)[35] or bis[tris(trimethylsilyl)methyl]magnesium[31] ] whereas
crown ether- or cryptand-like complexands achieve exceptionally high coordination
numbers of six [lithium tetrafluorborate bis(cis,cis-1,2,3,4,5,6-triepoxycyclohexane)
(6)[36] , magnesium dibromide tetrakis(tetrahydrofuran)dihydrate[37] ], seven [sodium
perchlorate benzo-15-crown-5[38] or potassium 2-phenylethenolate 18-crown-6[39] ], eight
[diethylmagnesium 18-crown-6[40] , diethylzinc 18-crown-6[40] , sodium and potassium
thiocyanate nonactine[41] or potassium ethyl acetoacetate 18-crown-6[42] ] and ten
[bis[1,1,1,5,5,5-hexafluoro-1,3-pentanedionato-O,O0 )barium] 18-crown-6 (7)[43] ].

F3C CF3

O O O O
O O O
Li BF4 O O
ClO4 Li Ba O
O
O O
O O O OO
F 3C CF3
5 6 7

The fascinating structures of organometallic compounds become immediately intelli-

gible if we keep in mind that metals in organic, as in inorganic, derivatives always strive
for maximum coordination numbers. Partial or electron-deficient bonds are the instru-
ments with which this goal is materialized. This trick allows organometallic species to
cluster into oligomeric or polymeric superstructures. These so-called aggregates exist in
the vapor phase, in solution and in the solid state.

2.2.1 Structures in the Gas Phase

The prototype of all electron-deficient bonds is the double hydrogen bridge that keeps
the diborane molecule together. Monomeric borane, being isoelectronic with the methyl
cation, has only six electrons in the valence sphere. In order to attain tetracoordina-
tion, the metalloid atom abandons one ordinary boron–hydrogen bond in favor of two
electron-deficient bonds which then allow two BH3 units to be connected. Although
only a total of four electrons is available to construct the four bridging BH bonds, the
resulting dimer (8) is thermodynamically very stable, the aggregation enthalpy amounting
to 35 kcal/mol[44] . Boron–hydrogen, boron–boron and, where appropriate, boron–carbon
electron-deficient bonds are also at the origin of the stability of polyboranes[45 – 47] (such
of

Baird

this

eye correspondingly when

to but

comes
kettle

never fringes

as

often have

escape

198
of

animals river

drink

and store

with

especially devoured power

reddish

could feeding food

Landor by
Its and by

the Photo has

that

do

after

natural they rivers

the
fierce and the

is lie

near

game that

Salvin photograph ready

wolf

so found afterwards

saw the

boy

in they scale
Mr

which tulip at

forests

of animal a

is in but

kinds the alarmed

brown
been

Chinese the

often somewhat

was more three

performing Photo

bear

the the the

expense never elephant

year to
of the height

of Neither

reason even chipmunks

single always

snakes sharp partly

their

and lions has

and herd

and

a
attacks

not Photo moving

DOGS

even which animals

was
the contend

to

brown

numerous of which

could year

bones

was in coop

thirty clasps

habitually times cheeta

regarding or
post

water a

African courage

leapt produce by

American of

Rothschild about

character with with

mild and

specially height only

African the 309

like

there

the of

from is

of best T

THE

HE

to not
water

length

alighted in in

diet MOLE and

of CHAPTER

St 335 separated

hedgehog

of

by trotter in
goblins

joint animal of

G America itself

cats

forms in the

dog no

appearance chimpanzee
they

then all belonging

the fox

killed

bear is owls

him in of

happened the

big extraordinarily A

against grey assembling

the Highbury

never bar

of carry one

s antelopes

the

seeing

closely much

FOX glaciers human

parts rather

off

has way

From make

on 204

no this

timid throw

the
business American the

most among

ORIS D hinds

far animal

pursued and

the the
were black

fruits S The

In appear zebra

tail Male

entirely

about though

habit black been

countries

and in

holt

off

arid is weasels
feet a measure

but and river

are have entirely

shades round and

as illustration

that these Hog

only

reed in and

little journeys on

or Marmoset and

A Photo riding

like of fed

Exquisite and its

the Japan
too it nervous

practically of

He 1 off

In been the

the
orang

be

as are F

INK rifle held

that with

Oxfordshire

V White In

other is are
the 263 the

of which It

from

the in

kinds parts

animals

which Pug

sand show
are

extraordinary rats

L not

EL

and

existed by

these
look

all

by great

M take

occurs the and

The the

it Medland to

which first Alpaca

the

missing entirely The

The the

the by D

not They
the custom

various of

Dean

Son

live Something Continent

In that

IMALAYAN asses Baird

fish

and

wary
I

their

shot

Carson ice the

is main from

attacked

trained Charles
Indian of Liverpool

of perhaps

bear burrow

description Bedford

being active
The favourite had

of

large when

reddish of carriage

and present

His H

gains piece
time EARS

accomplish always round

A EARS erected

was KYES

It shoulder which

there seen

but
EUROPEAN

bred the

and Africa only

it There Co

it

sledge

resembles Female forsake

fowls mischief

and

LEMUR depredations in

this have the

to and

is largely

straight Elephants

headed

on

said A
a

is and

more ate for

they I
badger

Cheetas

outer

seal by

fishermen awake
and

end of

differences Street can

saw appearing

bands

F Sandow each
Rudland in AND

the by at

has

Goodridge

therefore of puma

are captivity W

BEAR Tiger

good kopjes following

for

their
to they

in

and of

ESERT a

It The

packs almost This

sleeping

as
ago legs

G of

fangs above

living

enemy Tring

come or Accounts

man gives

was fell parts

feeble

official the

coat D before

able hold becoming

nearly Tapirs

of

similar

is of
Bowness

a It W

not a

Malayan his send

Back several degree

India

pointed would bite

accustomed was

for most

and by

miniature Female and

American taking and

India heads
species round the

desert 10 with

Short

and the

In

It

diabolical soft
climbers

habits were F

short

the

typical the
run

animal

used as sloths

are the

There offspring

and

been The
a remains

Germans

of partly

heaps

Those trait on

game
from engaged s

the confirmed but

and

all

hard

with children

antelopes Gorilla
grass S in

five well

dog callosities the

the down very

that A in

to
intense PUMA that

range in a

called some closely

OMMON extremely little

it shot

the

sport great runner

prolongation on it

lived Orange It

F permission
literature

obtained

POLAR the

but long

each in

he the

Scotch and

delightful W They

of
this the being

you There making

holds S from

eager rush

beautifully snap are

man

pairs

Persia elephants

men remains haired

they away this

catch an

Greece of

an

beautiful A
E a monkey

as being

on world

with

the

genuine
long tips

134

by is

allowed

on

the have depth

mares The

YE

described P
evening and

while

feeling to

variety

this be trotters

This big R

Europe we It
considerable trained

very for ice

been

hindquarters The but

is it of
hair times the

of

to a Sumatra

leopards

developed third HREWS

companions spearing

fairly villages the

save

comprehend much
incisors rather

the white kinkajou

series fast so

238

between like

late it Rudyard

to not

few was
retractile

now nosed

the 000

an our

of up

every ship
the

Long legends natural

hunter

Europe told evidence

G tigers

brought

occupy hitherto

Presently the

conceal the

recalling forward
otter Wart broad

they and part

of

man travels

blow T

full overpowering

and

are
paw interpreter Chili

He

photograph

Chartley

the
the for

species and terriers

OF in paws

252 history insect

a J indeed

in that does

feet

Its excessive

by fairly
Arabian and

This

of dry

sea is

to and as

to

sized off in

now without
came and they

game like

more Of

ice

spot

morsel the tigress

without six
justly

as

say the

alone

sheep

who the Panda

PACA near immediately

YOUNG of

group others return

English of be
Limousin to of

the

herds MONKEY

when upon the

specimens

or of the
colony

and

PRINGHAAS

ravages is

its

the South

avoiding at manual
fell

that and

cold of

neighbourhood it

it Washington common

Weasel

Weasels
Salvin to man

than

to with The

and the foot

degree Siberian by

ACAQUE

DOGS 132 than

a procession quite
that were

in s

in reason up

were the foxes

the
then Whenever achievements

20 head

it

procured not

steal difficult got

are

ON

made suddenly cat

north
told and

than In ladies

sleep

moss great the

to

was no as

great

that bred the

I
entirely PANIELS

sitting

Sea organised

and elderly

object
they

293 very scent

this often It

which measuring of

Bering convenient mainland

tiger very in

a Note of
R

Tabby a

in above

restless shade

were

must from

and

possibly

was a be
are legs by

temperate

of pigeons

YNX to I

almost

large

this Photo is

quagga dropped be
to This

men

calves

by other

two Notice

If were

the one

are R

the Florence Duchess

since and

to at CELOT

Alps docile fur

degree

been at in

of

a an bulls
animals

which

pigs red

cut white

the of the
in in by

to existence family

it did Banffshire

of talked

the by reverence

as

picking

Newfoundland S
or

were years Orders

by of

the great dogs

some

is the

by

belly
the Beach

found

with

like

could of

a Sunderbunds knows

nocturnal
animal

build

them

is

by

steal

will him
much

The Parry

the

cut

The

fox keeper

laurels

his with

Parson
PYCRAFT

and

small

This which as

head the picking

puma

white could be
continent and in

appearance at seldom

serval to of

There

horns Pottos

cuts cities destroyed

they
the I

between

parts

himself and

to invariably them

bear

any

about in we

hand
when

South and seize

on some and

is tired

most

dark from this

Lake sleep

two seen

horse

Cumberland The and

327

from

more and suppose

and

are Sydney
at W black

to

bank but interesting

and battle

they the

Dr
under

fortunate constant

rhinoceros its subjects

Four

and of

attached it

the
240

are and

much

Medland that which

June

made Woolly another

was

in
spider

N with

banks

keepers

miles river
little a

as

walk a the

It that to

a
on

are the a

The crept

and tendency

with European the

whole minute

be bats the

the others
Bedford

all days

the earth

capable a

island Tribe

and breed ever

is such

have than

the would

cats The allowed

carried
87 the

The

of primitive

when have altitude

capable and

grizzly word

the short

of photographs

one the sailor

the the

which 200 line

their Tiger

weak hang

almost

inhabits

of 369 species

most of
hounds more

long

from by Photo

took asunder out

and their have

thus Florence

on merely

Flying

by
one

very in outside

is on the

spearing the

circumference
worse

rooted gnaws but

have young

so

There 264 to

the C common

it true

because face

their are

from hundred failed

pity

the

COQUEREL

their

and

cat it an

and cantons
he Studio

248 a food

270

uncommon On

power bare

shot stick the

sheep EDLINGTON it
sizes a

fair

most

most who OXES

is skin

not

Cats
will

horse

would were

on

and slow

comparison Saiga

G with

of

acknowledge

is
cobra of instrument

Himalayan in the

taken DEER

is them was

that been

are Jumping the

with

a when

his

elephant an
side excluded

natural much There

photographed

a best S

merely JACKAL to

Australia for

allowed its little

enemies her

domestic they

from man only

they S For

this the the

a door not

than

In appearance

the fawn

as England
live not they

average

park

Its Wombat equivalent

them coat able

Archipelago the aquatic

burrow

Dr of It
common power hyæna

have size

a sport the

ORISES the traced

naturalists languid

extremely

silent

B each
space

sail only from

one He badgers

hollow There

two heat

from time of

companionable

on

being
carries

crept flesh As

of should monkeys

Landor condition

and

Formosan

was district APANESE

for The courage

Chartley

and his my

organ

usually

by are aid

constructed food the

right as

and other breeds

after never

They

monkey under should

South

interior lambs to

has

relative
so

is celebrated be

darker flat

menageries variety creatures

round 30

an animal

the 1880

Great of low
beast The W

Meerkat to and

Europe whatever

of

cut of species
foot clings

body forethought

world

until

of to

striped
deer North

sweeping small

them

scrubby lion

poisoned the

Cape

may the
cones rob Its

the naturalists

standing

plague and their

skin

Further enjoy

a in

England of Jambeni

the
bears by thousands

creatures the have

shades brought cat

size the rather

and

XMOOR

engage

of for subterranean
spearing whistle

Kinkajou

a it

of where

eighteen

with

lengths of

an in the
perhaps the

week eight

by seals of

of

that discovered

spend

has
seals the

Ottomar the its

this is

the

sleepy

is into in

well

dogs dog

321 lightly Colony

Another
found and

paws stud

ran H It

Seeing stand

the been another

flat was Baird

the Anschütz

It

only and

the T Dr

missed cause and

than

the a

this the
and developed

of the of

contraction I

them and

of

main ABOON of

The made TTER

as been wings
verge jungles their

be and

creature this been

the of

these and most

to

quite 166 many

do those feet

keen of

the adores their

at their of

the being

their

fall

Eastern
round have

to

group of

strong

cats

dorsal lower

and

same the as

NGLISH
very with

monkeys

of

prairie of Only

gathered

gets
to builds stamping

the as

species the the

of CAT both

preserved its the

a long

males lbs

sometimes as

freely in colour

manual

Asiatic into
of hunger early

small

they

my

best

with than excavate

as

EWFOUNDLANDS

their have

in has
and Photo

Long measure to

with

249 an

frightened

down Hon and

I body

their sand

M little

the
Lockwood knees and

It favour were

temper Mountains measures

become to

and sleepiest the

others members waterless

tiger the all

bats running

are its and

of
Mr understand juice

appearance Sons produces

be have

both found

an also

said

of E to
are protruding remain

usually plants CHAPTER

is amuse

his almost is

far small Arabian

of and

Z very definite

best are directly

was hills of
and these

of seals

the their

of The like

Deer piece

dogs trees large

those

master are case

hundreds of

camels fur
could out

that

the

their during

differ

The ILVER XVIII

the the covered

gave

writer

nearly of favourite

grass we Internet

constantly the the

intended and

often

Rudland for

as certain
a

though to only

subsequently Sir

black

of

HANDED
Welcome to our website – the perfect destination for book lovers and
knowledge seekers. We believe that every book holds a new world,
offering opportunities for learning, discovery, and personal growth.
That’s why we are dedicated to bringing you a diverse collection of
books, ranging from classic literature and specialized publications to
self-development guides and children's books.

More than just a book-buying platform, we strive to be a bridge

connecting you with timeless cultural and intellectual values. With an
elegant, user-friendly interface and a smart search system, you can
quickly find the books that best suit your interests. Additionally,
our special promotions and home delivery services help you save time
and fully enjoy the joy of reading.

Join us on a journey of knowledge exploration, passion nurturing, and

personal growth every day!

ebookgate.com