Organoderivatives of Rare Earth Elements

540 Pages·1995·29.267 MB·English

by  M. N. Bochkarev, L. N. Zakharov, G. S. Kalinina (auth.)

OrganoderivativesofRare Earth Elements
TOPICS IN f-ELEMENT CHEMISTRY
VOLUME 3
Editor
SHYAMAP.SINHA, UniversityofDayton, US.A.
EditorialAdvisoryBoard
J.L.ATWOOD, UniversityofAlabama, US.A.
W.J. EVANS, UniversityofCalifornia, Irvine, US.A.
M.F. LAPPERT, UniversityofSussex, Brighton, UK.
J.D. NAVRATIL, RockwellInternational, Golden, Colorado, US.A.
A.A. PINKERTON, UniversityofToledo, Ohio, US.A.
H. SCHUMANN, TechnischeUniversiUitBerlin, Berlin, Germany
Thetitlespublishedinthisseriesarelistedattheendofthisvolume.
Organoderivatives of
Rare Earth Elements
s.
M. N. BOCHKAREV, L N. ZAKHAROV and G. KALiNINA
Institute of Organometallic Chemisfry
Russian Academy of Sciences
Nizhny Novgorod, Russia
~.
"
SPRINGER SCIENCE+BUSINESS MEDIA, B.V.
Library of Congress Cataloging-in-Publication Data
Bochkarev, M. N.
Organoderlvatlves of rare earth elements I M.N. Bochkarev, L.N.
Zakharov, G.S. KaIInina.
p. cm. -- (Toplcs In f-ele.ent chealstry : v. 3)
Includes blbllographlcal references and Index.
ISBN 978-94-010-4161-4 ISBN 978-94-011-0361-9 (eBook)
DOI 10.1007/978-94-011-0361-9
1. Organorare earth metal co.pounds. I. Zakharov. L. N. (Leonld
Nlkolaevlch) 11. KaIInina, G. S. 111. Tltle. IV. Serles.
QD411.8.R37B63 1994
547' .0541--dc20 94-31169
ISBN 978-94-010-4161-4
This book is a revised and updated translation of the original work:
Organoderivatives of Rare Earth Elements, Moscow, Nauka @ 1989.
Printed on acid-free paper
All Rights Reserved
© 1995 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1995
Softcover reprint of the hardcover 1s t edition 1995
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
including photocopying, recording or by any information storage and
retrieval s~stem, without written permission from the copyright owner.
TABLE OF CONTENTS
Preface 1
Abbreviations 3
Introduction 5
Chapter I.
a-Alkyl and a-aryl complexes
1.1. Di- and trialkyl(aryl)lanthanoids
1.1.1. Compounds ofR2Ln type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 10
1.1.2. Compounds ofRLn type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 17
3
1.1.3. The RLnX derivatives 26
1.1.4. The RLnX2and R2LnX derivatives 30
1.2. Complexes ofate-type 34
1.3. Compounds with cyclopentadienyl and TJI-bonded ligands
1.3.1. Compounds ofCpLnR2type 46
1.3.2. Compounds ofCp2LnR type
1.3.2.1. Synthesis 54
1.3.2.2. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
1.3.2.3. Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
1.3.2.4. Reactivity . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . .. 84
1.3.3. Heterobimetallic complexes with bridging
hydrocarbon group
1.3.3.1. Lithium derivatives 87
1.3.3.2. Aluminium derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
1.4. Compounds with cyclooctatetraenyl and TJI-bonded ligands 99
1.5. Ylide and zwitterionic complexes " 101
References 107
Chapter II
TJ3-Allyl and similar complexes
11.1. Synthesis and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 122
11.2. Spectroscopic data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 135
References 136
v
Chapter III
Cyclopentadienyl derivatives
111.1. Dicyclopentadienyl complexes
111.1.1. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 138
111.1.2. Properties 145
I1I.1.3. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 148
I1I.IA. Spectral characteristic ofcomplexes 160
111.2. Tricyclopentadienyl complexes
111.2.1. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 162
111.2.2. Properties 166
I1I.2.3. Spectral characteristics 171
111.204. Structure . . . . . . . . .. 173
111.2.5. Mass-spectrometry and dissociation energy 180
111.3. Complexes with coordinate bonded ligands . . .. 183
lIT.... Halides and related compounds ofREM cyclopentadienides
I1IA.1. Dicyclopentadienyl derivatives
I1IA.l.1. Synthesis . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. 193
11104.1.2. Structure 203
I1IA.1.3. Properties 213
I1IA.2. Monocyclopentadienyl derivatives
111.4.2.1. Synthesis 215
11104.2.2. Structure 218
I1Io4.3. Spectral characteristic ofCP2LnX and
CpLnX2type complexes 220
m.5. Heterobimetallic complexes ofate-type . . . . . . . . . . . . . . . . . . . . . .. 222
References 234
Chapter IV
Complexes with the cyclic polyene ligands
IV.1. Indenyl complexes 250
IV.2. Fluorenyl complexes 255
IV.3. Cycloheptatrienyl complexes 257
IVA. Cyc100ctatetraenyl complexes
IV.4.l. Synthesis .. . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 258
IVA.2. Structure 263
IV04.3. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 269
IVAA. Spectral characteristic 270
IV. 5. Arene complexes oflanthanoids 273
References 285
VI
Chapter V
Organohydrides oflanthanoids
V.I. Synthesis 291
V.2. Structure 296
V.3. Properties 310
V.4. Spectral data 316
References 319
Chapter VI
Compounds with a Ln-N bond
VI.I. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 322
VI.2. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 333
VI.3. Properties 350
References 353
Chapter vn
Compounds with Ln-P and Ln-As bonds
VIT.1. Phosphorus derivatives . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. 358
VII.2. Arsenic derivatives 361
References 363
Chapter VIII
Compounds with a Ln-O bond
Vill.l. Alkoxides ofLn(OR)3 type
Vill.l.l. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 364
Vill.1.2. Properties and spectral characteristics 368
Vill.1.3. Structural cJ:taracterization 378
VIll.2. Halide/alkoxides ofREM and otherderivatives ofthe Ln(OR)3.•Y•
type 382
Vill.3. Alkoxides, oxides and hydroxides ofcyclopentadienyl
lanthanoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 395
VillA. Bimetallic alkoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 409
References 417
Chapter IX
The compounds with alanthanoid-chalcogen bond
IX.1. Synthesis and properties 424
VII
IX.2. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430
References 434
Chapter X
Compounds with lanthanoid-metal bonds
X.1. The derivatives ofnontransition metals 436
X.2. Complexes ofREM with carbonyls and nitrosyls of
transition metals 452
References 471
Chapter XI
Complexes ofCe(IV) 477
References 483
Chapter XII
Miscellaneous compounds
xn.I. Carbonyls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 485
XII.2. Graphite intercalates 487
XII.3. Phthalocyanines and porphyrins 488
XII.4. Complexes with other nitrogen containing ligands . . . . . . . . . . . . . .. 494
xn.s. Products ofgas phase reactions ofLn+ with hydrocarbons 495
Xn.6. Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 496
References 498
Chapter XIII
Applications oforganolanthanoids
Xli.I. Catalysis ofpolymerization 508
Xli.2. Catalysts and reagents for reduction
and oxidation processes 511
Xli.3. Miscellaneous applications ofREM compounds 514
References 516
Index 524
Vli
PREFACE
The present book is based on the work of M.N.Bochkarev, G.S.Kalinina, L.N.
zakharov and S.Ya.Khorshev. The Russian edition of that book appeared under the
same title in 1989 and covered literature data up to the middle of 1986. Since that
time the number of publications on this subject increased significantly. In this volume
we include all the data published up to the end of 1990, as well as some of the most
important relevant articles of 1991. Therefore, this book should be considered as a
new book, devoted to the same problems, rather than as just a translation of the
mentioned issue.
This book deals with compounds of scandium, yttrium, lanthanum and lanthanoids
containing direct metal-carbon bond, Le. with the real organometallic complexes of
these metals. Besides, the volume includes the rare earth complexes, in which organic
ligand is bonded to the metal atom via the atom of another element of the Periodic
Table. In other words, the book includes all classes of rare earth organoderivatives.
Carboxilates, fl-diketonates and related chelates are the exceptions, because their
properties are closer to inorganic compounds and they were fully described elsewhere.
It should be noted, that "rare earth elements", "rare earth metals", "lanthanoids" and
related terms are used in this book for indicating scandium, yttrium, lanthanum and
the following 14elements ofthe Periodic Table.
The main attention is paid to the methods of synthesis, molecular structure and
chemical properties of named compounds, although some knowledge on spectroscopy
and other physical properties are also summarised.
The compounds in this book are classified according to the type of ligands of
lanthanoid atom and the accepted order ofChapters follows the same principle.
In the last section we show the fields of practical application of organolanthanoids as
well as inorganic compounds in case they are used in organic synthesis, in which the
formation oforganometallic intermediates is expected.
Almost every chapter contains tables with the shortly cited properties of
organolanthanoids. As a rule, the tables include the compounds, which are isolated and
characterized by elemental analysis, mass-spectrometry and X-ray diffractometry,
although all the otherless characterized complexes are given in the text as well.
The collection and consideration of X-ray data in all chapters of this book have been
done by L.N.Zakharov. Chapter II and sections 1, 2, 3 and 4 ofChapter IV have been
written by G.S.Kalinina. Writing of the other chapters and sections and editing of the
book have been performed by M.N.Bochkarev.
The authors are grateful to many colleagues from the Laboratory of Polynuclear
Organometallics of the Institute of Organometallic Chemistry of Russian Academy of
Sciences and the X-ray Structural Centre ofGeneral and Technical Chemistry Division
of Russian Academy of Sciences for the assistance and encouragement during the
period of writing this book. In particular, the authors wish to thank Dr. Stanislav Ya.
Khorshev, who took a big part in writing the previous Russian issue and rendered a
big technical help in the preparation ofthis volume.
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