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Book Review Comprehensive Organometallic Chemistry. The Synthesis Reactions and Structures of Organometallic Compounds. Nine volumes. Editors G. Wilkinson F. G. A. Stone E. W

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chromatography. In contrast the new route is not only
trans-selective, but uses simpler starting materials, proceeds under milder conditions, and allows a doubling of
the overall yield (ca. 37% for the steps 8- 9- 10- 12).
Received: June 7, 1983; revised: July 18, 1983 [Z 414 IE]
German version: Angew. Chem. 95 (1983) 796
CAS Registry numbers:
1, 64854-44-0; 2a, 123-72-8; 2b, 24108-29-0; 3a, 18020-64-9; 3b, 87050-26-8;
4a, 87050-27-9; 4b, 87050-28-0; Sa, 16493-96-2;5b, 34312-78-2; 6a, 8705038-2; 7a, 3070-68-6; Ea, 22927-31-7; 8b, 87050-29-1; 9a, 87050-30-4; 9b,
87050-31-5; 10n, 87050-32-6; lob, 87050-33-7; l l a , 87050-34-8; 12% 8705035-9; 12b, 87050-36-0; 13a, 87098-85-9; 13b, 87050-37-1; DABCO. 280-57-9;
methyl acrylate, 96-33-3
I l a (32%)
9a (95%)
9 b (92%)
10a (92%)
10b ( 8 9 % )
12a (C: 45%; E : 6070)
12b (C: 42%)
b, R = CH3
Scheme 1. A ) acrylic ester, DABCO (cat.). RT; B ) NBS (N-bromosuccinimide), Me,S; C) 1. HSiC13, NEts, CuI, 0°C-RT [Sd]; 2. 8 Equiv. MeLi,
-60-0°C: 0)8a was added to the Horner reagent prepared as follows: 1.
(Et0)2P(0)CH,C0,Et + NaH in 1,2-dimethoxyethane; 2. Me3SiCH21,70°C
4 h; 3. NaH, 0°C-RT, thereafter 0°C (and addition of 823, 0°C-RT, 16 h);
E ) SMeLi, -60-0°C.
[I] H. M. R. Hoffmann, J. Rabe, Angew. Chem. 95 (1983) 795; Angew. Chem.
Int. Ed. Engl. 22 (1983) 795.
[2] See e. g. E. Rodriguez, G. H. N. Towers, J. C . Mitchell, Phytochemistry I5
(1976) 1573.
[3] a) B. Maurer, G. Ohloff, J . Chem. SOC.Chem. Commun. 1977, 353; b) P.
Dubs, H. P. Schenk, Helu. Chim. Acta 61 (1978) 984; c) J. P. Morizur, J.
Tortajada, Tetrahedron Lett. 23 (1982) 5275; d) see also L. C. Rohela, R.
C. Anand, Indinn J . Chem. 1 6 8 (1978) 1121.
[4] a) Cf. J. A. Bulat, H. J. Liu, Can. J . Chem. 54 (1976) 3869. Oxidation of
the alcohol to the aldehyde was simplified by using buffered pyridinium
chlorochromate; b) S . Krishnamurty, H. C. Brown, J. Urg. Chem. 45
(1980) 849; see also S. Krishnamurty, Aldrichim. Acta 7 (1974) 55; c) H. J.
Liu, L. K. Ho, Can. J . Chem. 61 (1983) 632; d) review: R. M. Magid, Tetrahedron 36 (1980) 1901.
[5] a) Newer methods far the synthesis of trisubstituted double bonds: A.
Marfat, P. R. McGuirk, P. Helquist, J. Urg. Chem. 44 (1979) 3888 and references therein; J. F. Normant, A. Alexakis, Synthesis 1981, 841; J. E.
McMurry, J. R. Matz, Tetrahedron Lett. 23 (1982) 2723; b) H. M. R. Hoffmann, R. Henning, Heh. Chim. Acta 66 (1983) 828; c) J. Rabe, Dissertation, UniversitBt Hannover 1983; d) H. Nishiyama, H. Yokoyama, S. Narimatsu, K. Itoh, Tetrahedron Lett. 23 (1982) 1267.
Comprehensive Organometallic Chemistry. The Synthesis,
Reactions and Structures of Organometallic Compounds.
Nine Volumes. Editors G. Wilkinson, F. G. A. Stone, E.
W. Abel, Pergamon Press, Oxford 1982. Total ca. 8500
pp., bound, E 1075.00.
Volume 1
The first volume (754 pp) of this exceptional work deals
with the organoelement compounds of the 1st to the 3rd
main groups of the periodic table. Even though the most
spectacular developments since 1950 have been more in
the area of the transition metals, the chemistry of the main
group elements has also developed very rapidly and has
stood in need of an adequate modern treatment for some
time. Although the aim of the authors to provide a comprehensive coverage of a given field is of its nature unattainable, they have, nevertheless, performed an excellent service
within the framework of this series.
Fourteen authors have contributed to this first volume,
most of whom are especially active workers in their respective fields. Astonishingly the result is a work with a rather
homogeneous style, evidently attributable to the editors.
Angew. Chem. In:. Ed. Engl. 22 (1983) No. 10
The volume begins with an informative chapter by M. E.
O’NeilZ and K. Wade (University of Durham): Structural
and Bonding Relationships among Main Group Organometallic Compounds (42 pages, 207 references). The most
important structural and bonding types for organometallic
compounds of the main group elements are presented using examples. Emphasis is placed on the bridge structures
of the oligomeric organolithium and organoaluminum
compounds, and on the polyhedral structures characteristic
of the carbaboranes and metallacarbaboranes. The subsequent chapters deal with the chemistry of the individual elements: J. L. Wardell (University of Aberdeen): Alkali
Metals (78 pages, 321 references); N. A. Bell (Sheffield
City Polytechnic): Beryllium (34 pages, 260 references); W .
E. Lindsell (Heriot-Watt University): Magnesium, Calcium, Strontium and Barium (98 pages, 635 references); J.
D. Odom (University of South Carolina): Non-cyclic
Three and Four Coordinated Boron Compounds (58
pages, 591 references); J. H. Morris (University of StrathClyde): Boron in Ring Systems (70 pages, 484 references);
G. E. Herberich (Technische Hochschule Aachen): Boron
Ring Systems as Ligands to Metals (30 pages, 90 refer797
ences); T. Onak (California State University): Polyhedral
Organoboranes (48 pages, 247 references); R . N . Grimes
(University of Virginia): Metallacarboranes and Metallaboranes (84 pages, 260 references); L. J. Todd (Indiana
University): Heterocarboranes (12 pages, 7 1 references); J.
J. Eisch (State University of New York): Aluminum (128
pages, 742 references); D. G. Tuck (University of Windsor): Gallium and Indium (52 pages, 282 references); H .
Kurosawa (Osaka University): Thallium (29 pages, 143 references). Each chapter ends with a reference list covering
the literature up to about 1980. The whole is a somewhat
capricious, but nevertheless very useful compilation of
very variable profundity. The compounds of Li, Mg, B,
and Al are emphasized as becomes their importance. It
should also be taken into account that their application in
organic synthesis is the subject of most of Volume 7.
The contributions do not follow any regular pattern, but,
nonetheless, regularly contain sections on the formation,
structure and reactions of the compounds concerned.
More detailed information concerning synthesis is still to
be found in the relevant volume of “Houben-Weyl”; here,
as also with “Gmelin”, there is a not yet complete but updated new edition covering organoboron chemistry. A particularly valuable feature of Volume 1 of “Comprehensive
Organometallic Chemistry”-and this applies to the other
volumes too-is the information concerning questions of
structure and bonding. Taken with the extraordinarily useful index volume the book is a regular treasure-trove and
stimulates to repeated delving and reading. The stated intention of the editors to initiate new ideas and further discoveries is likely to meet with real success. The whole work
is aimed at the worker engaged in basic research. Over and
above this it will be a first-class source of information for
all chemists and that for a long time to come. The desirable
dissemination of the work is, however, impossible at a total
price of more than DM 5000.-. The opportunity to buy
individual volumes is, therefore, urgently necessary.
Erwin Weiss
Institut fur Anorganische und Angewandte Chemie
der Universitat Hamburg
Volume 2
The second volume of this nine-volume work comprises
thirteen chapters dealing with very different areas of organoelement chemistry, so that the volume seems, at first
sight, to be very heterogeneous. This is because of its character as a reference work which does not offer a systematic
treatment of the material. However, this first impression is
soon forgotten as a consequence of the quality and the independence of the individual sections.
The first four chapters are devoted to organosilicon
chemistry: D. A . Armitage (University of London): Organosilanes (203 pages, 752 references); T. J. Barton (Iowa
State University): Carbacyclic Silanes (99 pages, 415 references) R . West (University of Wisconsin): Organopolysilanes (33 pages, 136 references); F. 0. Stark et al. (Dow
Coming Corporation): Silicones (59 pages, 193 references). This arrangement seems somewhat arbitrary and
naturally leads to overlapping. However, since almost every author has been successfully active in his respective
field, the contributions are so stamped with a genuine understanding that their study is, nevertheless, of great value
in each case. This is also particularly true for the article on
the present state of silicone chemistry in industry, which
emphasizes the practical importance of organosilicon compounds and summarizes the newest technical developments, briefly but informatively.
The chapters on the organometallic compounds of germanium (120 pages, 716 references) by J. Satge et al. (Universite Paul Sabatier, Toulouse), tin (109 pages, 722 references) by A. G. Dauies and P. J. Smith (University College,
London, and ITRI, Greenford) and lead (52 pages, 419
references) by P. G. Harrison (University of Nottingham)
come likewise from laboratories which have made significant contributions to the developments discussed. Naturally only the highlights of the literature could be included: After all organotin chemistry now fills fifteen volumes of Gmelin!
The organoelement compounds of arsenic, antimony
and bismuth are described (by J. L. Wardell, University of
Aberdeen) on only 27 pages (179 references), which necessarily leads to a loss of quality. The expectations of the
reader are greatly disappointed in this section; the relative
importance of this area is not properly represented, a fact
which affects the value of the whole work. Perhaps arsenic
(and antimony) should rather have been omitted altogether.
The coinage metals copper, silver and gold are treated in
a manner which takes account of the rapidly increasing importance of these elements; the first two by J . G. Noltes
and G. van Koten (TNO Utrecht and University of Amsterdam and the third by R . J. Puddephatt (University of Western
Ontario), in 55 pages (187 references) and 57 pages (227
references) respectively; here again the competence of the
authors is happily apparent. The workers mentioned had
already produced the previous leading monographs on the
same topics. Finally, there are chapters on the organometallic compounds of zinc and cadmium (J. Boersma, UniversitCt Utrecht; 40 pages, 163 references) and mercury (J.
L. WardeZl, University of Aberdeen; 116 pages, 545 references) which are certainly correctly placed alongside the
coinage metals.
A concluding contribution from P. J. Craig (Leicester
Polytechnic): Environmental Aspects of Oranometallic
Chemistry (42 pages, 319 references) attempts to set out
the more important aspects of the occurrence and effects
of toxic (natural and anthropogenic) organometallic derivatives in the environment. Unfortunately the well-known
“black sheep”, mercury, lead, tin and arsenic, steal so
much of the limelight that the desire for information concerning the environmental problems caused by the other
elements is scarcely considered. Nevertheless, this chapter
is worthy of note and is quite useful as a basis for teaching
The external appearance of the volume, together with
the quality of the print, are impeccable, and study is simplified by the attractive distribution of text, formulas, figures and tables. The literature is cited up to the most recent
times in most of the contributions, so that this collected
work will retain its topicality for some years. The inevitable transcription and typesetting errors (e.g . wrongly
spelled names in the author index) have been kept to a
minimum. Even the surname of the reviewer, which is particularly at risk, was rarely incorrectly spelled.
Hubert Schmidbaur
Anorganisch-chemisches Institut der
Technischen Universitat Munchen
Volume 3
The third volume (1384 pages) comprises ten chapters,
of which the first two are devoted to general problems and
the others to the organometallic compounds of the elements of the 3rd to 6th subgroups of the periodic table as
well as of the lanthanoids and actinoids. This mass of maAngew. Chem. Int. Ed. Engl. 22 (1983)No. I0
terial is successfully crammed in, thanks largely to the expertise of most of the authors.
Volume 3 begins with a contribution from D.M. P. Mingos (Oxford University): Bonding of Unsaturated Organic
Molecules to Transition Metals (88 pages, 55 1 references),
which is mainly classified according to the type of ligands.
Metal carbonyls, sandwich compounds, olefin- and alkyne-complexes, alkyl-, carbene- and carbyne-metal compounds are dealt with in separate sections. In addition, important types of reaction such as oxidative addition and reductive elimination, CO and alkene insertion, ZieglerNatta polymerization and olefin metathesis are discussed.
The author presents modem concepts in an instructive
manner starting from simple bonding concepts (e.g. those
of Dewar, Chatt and Duncanson for metal-olefin complexes) and compares the results of calculations (both ab
initio and semi-empirical) with experimental data, from
UPS measurements for example. Correlations, like those
which emerge through the isolobal principle, are also mentioned.
B. E. Munn (University of Sheffield): Non-rigidity in
Organometallic Compounds (83 pages, 185 references) in
the second chapter deals first of all with the methods of
studying fluxional structures. The extensive information
that follows concerning the results obtained up to now
(mostly in tabulated form) covers not only the rotation of
C, (alkyl, carbene) but also of C, ligands (alkene, alkyne,
di- and triene, allyl, cyclopentadienyl, arene) about the
axis of the metal-ligand bond, together with intramolecular
ligand exchange, the dynamics of o-ally1 and o-cyclopentadienyl compounds, the rearrangement of qz- to q6-cyclic
ligands (e.g . C7H7,CsHs, C8HIO)at metals and, above all,
the fluxional behavior of organic groups on metal clusters.
Mechanistic considerations are mentioned, but their understanding requires a careful study of the cited literature.
The other eight “systematic” chapters are arranged according to the placing of the metal in the periodic table. It
is pleasant to see that the elements scandium, yttrium, lanthanum as well as the lanthanoids and actinoids are not
treated as exotica and pushed into a corner, but that they
are given the place they now deserve. The organometallic
compounds of the 4f and 5f elements have come into the
sphere of general interest more than almost any other area
in the last decade, and that largely because of the work of
one of the authors, T. J. Marks. Of the remaining cu. 1100
pages about 280 are devoted to titanium and about 600
pages to the elements of the 6th subgroup (Cr, Mo, W);
thus, the extent of this presentation alone reflects the technological importance of the organometallic compounds
concerned. The flood of information (e.g. just on compounds derived from (CsHs)zTiC1zor Cr(CO),) is also presented in part in tabular form, thus facilitating a general
overview. The section on “Ziegler-Natta Catalysis” is particularIy worthy of mention (pp. 475-547) and deals not
only with industrially important aspects but also with the
results of model studies and mechanistic considerations. It
is also pleasing that even the, as yet, not so well developed
fields, such as the compounds of zirconium, hafnium or of
niobium and tantalum, have attracted prominent authors
(such as M . F. Luppert and J. A . Labinger) who have
played a leading part in the development.
The general impression given by this herculean publication: First-rate! Competent, comprehensive, well-illustrated (with, however, some superfluous ORTEP diagrams)
with few printing errors (mainly in the literature references). It is to be hoped by all those who are interested-in
Angew. Chern. In,. Ed. Engl. 22 (1983) No. 10
industry and in university-that, in spite of the present
miserable financial climate, this work will soon be available in all libraries.
Helmut Werner
Institut fur Anorganische Chemie
der Universitat Wurzburg
Volume 4
The fourth volume fits perfectly into this monumental
work and comprises seventeen chapters (1064 pages). P. M .
Treichel (University of Wisconsin-Madison) describes the
organometallic chemistry of manganese in a well laid out
manner and with a sure nose for quality and balance (147
pages, 649 references). The treatment of the homologous
elements technetium and rhenium (80 pages, 532 references) by N . M . Boug and H . D. Kaesz (University of California at Los Angeles) is of its very nature more modest
but, nevertheless, competent and informative. Apart from
the little studied technetium, there are numerous excellent
examples of the vast differences in chemical behavior between the corresponding manganese and rhenium compounds. In view of the tidal wave of data which has
poured out concerning iron since the renaissance in organometallic chemistry, the editors were well advised in
their decision to divide it into five chapters. D. F Shriuer
(Northwestern University, Evanston), K . H. Whitmire, A .
D. Johnson (University College London), A . J. Deeming
(University College London), W . P. Fehlhammer, H . Stolzenberg (University of Erlangen-Nurnberg) and J. L. Duoidson (Heriot-Watt-University) put across the substantial
essence over 400 pages (1477 references), whereby the individual treatments of iron complexes with various hydrocarbon ligands complement each other well and seldom
overlap unnecessarily. The chemistry of organoruthenium
compounds is divided between M . I . Bruce (University of
Adelaide) and M . A . Bennett (Australian National University), who present their chosen classes of compound with
experienced pens. Each of these nine contributions (Chap.
32.1-32.9) is rich in content but, thanks to the strict classification, easy to read. The chapter dealing with the chemistry of dodecacarbonyltriruthenium could be taken as a
model for disciplined selection of material. The contribution by M . A . Bennett and T. W. Matheson (Chap. 32.9)
gives an almost textbook review of the manifold, catalytic
aspects of organometallic ruthenium complexes. Volume 4
finishes with the element osmium: R . D. Adums (Yale University) and J . E. Seiegue (University of Kentucky) expertly describe, in particular, the modem aspects of this
chemistry, using the same sensible classification system
(carbonyl complexes, mononuclear complexes, cluster
complexes) used in the previous chapters as a framework,
whereby the treatment of trinuclear carbonyl derivatives is
worth particular attention and is a regular treasure-trove of
current results. The description of the fascinating osmium
clusters of higher nuclearity (Section 33.3.6) could have
been more detailed.
Not only the good scientific quality of this volume is impressive but also its presentation, with the exception of the
occasional overlarge formulas (e.9. pp. 644, 647). The multinuclear complexes with complicated ligands, in particular, should have been drawn in perspective, which would
often make understanding easier for the reader (e.g. pp.
899, 901, 905). The preparatively oriented chemist will
sometimes miss an explicit recommendation of the best
synthetic route; in this connection the key compound
(q5-CsH5)Mn(CO), is incorrectly reported (p. 124; cf. G.
Bauer : Handbuch der Praparativen Anorganischen Chemie,
3rd edition, Vol. 3, p. 1866ff, Enke, Stuttgart 1982). In general, however, the fourth volume lives up to the proud record of this modern encyclopedia-indispensable for the
specialist, helpful to those in related fields, a masterpiece!
Wolfgang A. Herrmann
Institut fur Anorganische Chemie
der Universitat Frankfurt am Main
Volume 5
The fifth volume (628 pages) of the series reviews the organometallic chemistry of cobalt (276 pages, 809 references), rhodium (264 pages, 1311 references) and iridium
(88 pages, 512 references); the authors are R. D . W . Kemmitt and D. R . Russel (University of Leicester), R. P.
Hughes (Dartmouth College) and G. J. Leigh and R . L.
Richards (University of Sussex) respectively.
The chapters dealing with cobalt and rhodium compounds begin with a suitable historical retrospect. All three
chapters are essentially based on the following scheme :
carbonyl, carbonyl hydride, thiocarbonyl, carbon disulfide,
isocyanide, nitrosyl complexes, divided each time into
mono- and multi-nuclear compounds, then follow the
complexes with o-bonded hydrocarbons (alkyl and aryl
compounds), carbene, alkylidene as well as carbyne and
alkylidyne complexes and then, finally, the compounds
with n-bonded hydrocarbons, classified according to the
number of carbon atoms which are bonded to the metal
(alkene, aIkyne, allyl, diene and cyclobutadiene, cyclopentadienyl, arene ligands). The individual sections are, in the
main, subdivided according to preparation, structure,
properties and the reactivities of the compounds. The literature is covered for the 25 years up to the end of 1979 together with some references from 1980. Organocobalt(II1)
systems (cobaloximes) are discussed in detail as models for
vitamin BIZ.The many tables (more than 100) in which
analogous compounds are summarized together with their
methods of preparation, spectroscopic data (IR, NMR) are
particularly valuable, as are the large numbers (1816) of
clear illustrations of formulas and schemes concerning the
structure, synthesis and reactivities of the compounds. Catalytic aspects are treated only briefly; these are dealt with
in Volume 8.
This series illustrates once more the stormy development
of organometallic chemistry since the discovery of ferrocene. The authors and editors have performed excellent
work in their critical sifting of the immense body of results,
it could scarcely have been done better. Volume 5 is at the
moment probably the best source of information in its field
for both newcomer and initiate. A treasure-trove of stimulation and, without question, a standard work for every library.
Wolfgang Beck
Institut fur Anorganische Chemie
der Universitat Munchen
Volume 6
Two thirds of the sixth volume (1114 pages) are filled
with complexes of the Ni, Pd, Pt triad. The rest is devoted
to compounds containing heteronuclear bonds between
different metals.
All three chapters concerning the organometallic chemistry of nickel, palladium and platinum are written by wellknown authors, who had already made names for themselves in the early seventies with monographs devoted to
their favorite metal. This explains, on the one hand, the retention with only slight modifications of the well-established classification of the material and, on the other hand,
the concentration on the latest results and tendencies. Thus
in the first chapter (231 pages, 50 tables), P. W . Jolly (MaxPlanck-Institut fur Kohlenforschung, Miilheim a. d. Ruhr)
has deliberately built upon the foundations of Volume 1 of
“The Organic Chemistry of Nickel” (P. W . Jolh and G.
Wilke, Academic Press, New York 1974); in many of the
tables it is noted that earlier work is reviewed in this book.
Also the second chapter (237 pages, 13 tables) written by P.
M . Maitlis, (University of Sheffield), P.Espinet (University
of Saragossa) and M. J . H. Russell (Johnson Matthey Research Centre) is obviously built on the foundations of
Volume One of “The Organic Chemistry of Palladium” (P.
M . Maitlis, Academic Press, New York 1971). Similarly in
the third chapter (289 pages, 47 tables) F. R. Hartley
(Royal Military College of Science, Shrivenham) can refer
to his monograph “The Chemistry of Platinum and Palladium” (Applied Science, London 1973). These contributions are excellently written and well illustrated by formulas; the density of information is very high. Although
members of a large team the authors have been able to retain their own personal styles and their individual methods
of presentation. Thus,’ the fifty tables of the first chapter
give a quick picture of the known organonickel complexes
(with appropriate references). In contrast the tables in both
the following contributions serve more to present spectroscopic and other data pertaining to selected palladium and
platinum complexes. The chapters on nickel and palladium offer the literature references portionwise at the end
of each of the nine sections, while for the chapter on platinum they are collected together into one comprehensive
list (1702 references). The fact that the editors did obviously not try to exert a levelling influence on their authors makes a favorable impression; the three individual
chapters can certainly be considered as small, independent
monographs. (Incidentally the use of nickel and palladium
in organic synthesis is described separately in Chapter 8.)
In the last part of Volume 6 the dilemma becomes evident which is necessarily faced on considering the systematics of complexes with two or more different metals, as
long as the chemistry of organometallic compounds is classified according to the metal. The problem of heteronuclear compounds has, however, been elegantly solvedwithout arbitrary definitions of priority. Compounds with
heteronuclear bonds between transition metals are dealt
with in a detailed chapter (115 pages, 13 tables) by D. A .
Roberts and G . L. Geoffroy (Pennsylvania State University); the emphasis is not on individual complexes but on
general synthetic procedures, spectroscopic methods and
the (at the moment rather sparse) investigations of reactivity. The main body of information is collected in three long
tables at the end of the chapter, which-divided into binuclear complexes, oligomeric compounds and clusterscontain data on all heteronuclear complexes with at least
one bond between two different transition metals known
before August 1980. These tables and the pertinent references take up 49 pages (42% of the total chapter); they
seem likely to become a much cited literature source, since
heterometal complexes are of topical importance as potential catalysts. However, it is by no means easy to confirm
unequivocally the presence of a metal-metal bond in all
cases. The last three chapters offer reviews, taking up 235
pages, of multinuclear complexes, where the bonding of a
transition metal occurs to a representative element, such as
boron ( K . B. Gilbert, S . K . Boocock, and S . G. Shore, Ohio
Angew. Chem. Int. Ed. Engl. 22 (1983) NO. 10
State University), aluminum, gallium, indium, and thallium ( S . K . Boocock and S . G . Shore), mercury, cadmium,
zinc and magnesium (J. M . Burlitch, Cornell University) or
silicon, germanium, tin and lead ( K . M . Mackay and B. K .
Nicholson, University of Waikato). The order of the sections is not particularly evident. The separation of boron
(Chap. 41.1; 67 pages, 22 tables, 289 references) is justified
by the structural variety of the boron-containing ligands ;
structures with up to 18 boron atoms are described. In
comparison with boron the organometallic chemistry of its
heavier homologues is significantly restricted, although
many interesting bond types occur.
Max Herberhold
Laboratorium fur Anorganische Chemie
der Universitat Bayreuth
Volume 7
Volume 7 (729 pages) of the series is devoted to the use
of organometallic reagents in organic synthesis. Lithium-,
alkali- and alkaline earth-containing reagents are dealt
with by B. J. Wakefield (University of Salford), and the application of organoboron compounds by authors from H .
C. Brown’s school, namely E. I. Negishi (Purdue University) and M . Zaidlewicz (N. Copernicus University, Thorn).
Organoaluminum compounds are reviewed by J. R . Zietz,
G . C. Robinson and K . L . Lindsay (Ethyl Corporation),
while the use of thallium compounds is dealt with by the
protagonists of the field, R . McKillop (University of East
Anglia) and E. C. Taylor (Princeton University). A further
chapter is devoted to a comprehensive treatment of organosilicon compounds by P. D . Magnus, T. Sarkar and S .
Djuric (Ohio State University). The work concludes with
an overview of the applications of zinc, cadmium, mercury, copper, silver and gold compounds in organic synthesis
by W. Carruthers (University of Exeter). Of the monohapto
organometallic derivatives which have acquired wider preparative importance, those of tin and titanium are notably
The volume is divided according to the key metals and
to the reagents derived from them. This classification principle assumes that the reader already has a basic knowledge of the typical reactivities of these reagents. For, if he
does not know, e.g., that alkyl cuprates add particularly
well to alkynes, when searching for such a reaction he is
unlikely to stumble across it in Chapter 49, whether he
uses the index or not. On the hand, if already armed with
this knowledge before consulting the present volume, he
will find a concise and precise exposition of the possibilities and limits for the use of the well-known homo- and
hetero-cuprates and analogous copper(1) derivatives,
which is precisely the information that is of help to him as
a potential user. Such assistance is necessary in view of the
enormous progress made in the last 25 years with organometallic reagents in organic synthesis: A look at the detailed documentation of “Houben-Weyl” or “Gmelin” in
the case of organoboron chemistry illustrates how extensive the results already are. This is just where the utility of
the present volume becomes apparent; it enables one to
quickly familiarize oneself with the areas it deals with.
Commendable are the chapters on organolithium, organoboron and organosilicon compounds; despite the flood of
original publications cited they are still comprehensible
and readable. Individually the text and the formulas make
up a well balanced whole, and the numbers of mistakes in
the formulas are minimal. Most of the chapters are written
in such a manner as to stimulate voluntary reading which
Angew. Chem Int. Ed. Engl. 22 (1983) hb.10
is rewarded with information and ideas that had previously been overlooked. The editors have, therefore, fulfilled their intention of creating a compendium which is
very stimulating to study. Since this volume provides an
ideal method of quick orientation in the application of organometallic reagents to organic synthesis, most organic
chemists would be pleased to have at hand, if not the
whole series, at least Volumes 7 and 8. However, only a
few of them are likely to have a patron in the background
and so most of them will have to use the well-thumbed library copy.
Reinhard W . Hoffmann
Fachbereich Chemie der Universitat Marburg
Volume 8
The eighth volume (1106 pages) contains the following
contributions: R . P. A . Sneeden (C.N.R.S., Villeurbanne):
Preparation and Purification of Carbon Dioxide and Carbon Monoxide (17 pages, 44 references); R. P. A . Sneedenr
Organic Syntheses where Carbon Monoxide is the Unique
Source of Carbon (82 pages, 343 references); I . Tkatchenko
(C.N.R.S., Villeurbanne): Synthesis with Carbon Monoxide and a Petroleum Product (123 pages, 185 references);
R . P. A. Sneedenr Reactions of Carbon Dioxide (58 pages,
202 references); B. R . James (University of British Columbia): Addition of Hydrogen and Hydrogen Cyanide to
Carbon-Carbon Double and Triple Bonds (85 pages, 525
references); W . Keim, A. Behr, M . Roeper (Technische
Hochschule Aachen): Alkene and Alkyne Oligomerization
Cooligomerization and Telomerization Reactions (91
pages, 491 references); H . B. Kagan (Universite ParisSud): Asymmetric Synthesis using Organometallic Catalysts (36 pages, 125 references); R . H. Grubbs (California
Institute of Technology): Alkene and Alkyne Metathesis
Reactions (53 pages, 146 references); C. U. Pittman Jr.
(University of Alabama): Polymer Supported Catalysts (58
pages, 346 references); P. W . Jolly (Max-Planck-Institut
fur Kohlenforschung, Mulheim a. d. Ruhr): Organonickel
Compounds in Organic Synthesis (182 pages, 1210 references); B. M . Trost, T. R . Verhoeuen (University of Wisconsin and Merck, Sharp and Dohme Research Laboratories, Rahway): Organopalladium Compounds in Organic
Synthesis and in Catalysis (140 pages, 805 references); A .
J. Pearson (University of Cambridge): Organoiron Compounds in Stoichiometric Organic Synthesis (73 pages, 23 1
references); W . E. Watts (New University of Ulster): The
Organic Chemistry of Metal-coordinated Cyclopentadienyl
and Arene Ligands (59 pages, 355 references); J. R . Dilworth, R . L. Richards (A.R.C. Unit of Nitrogen Fixation,
University of Sussex): Reactions of Dinitrogen Promoted
by Transition Metal Compounds (34 pages, 119 references).
As can be seen from the list of contents, Volume 8 is
mainly concerned with very topical applications of transition metal compounds, both as stoichiometric reagents and
as catalysts in organic synthesis. In spite of the size of the
volume and the fact that two related chapters (ZieglerNatta catalysis and the catalytic applications of ruthenium
complexes) are dealt with in other volumes (3 and 4) of the
work the perspective is incomplete. Some topics, e . g . oxidation, isomerization, rearrangement reactions and other
synthetic steps with organometallic compounds of the first
row transition metals, are only dealt with (if at all) in a cursory manner. The division of the contents into chapters
that describe either reaction types or the use of particular
metals results in some repetition and overlapping; this,
80 1
however, is not serious. The individual contributions are
from competent authors. The already enormous numbers
of references at the ends of the chapters are further augmented by references in the many tables. The patent literature is also included.
The three most important aspects of the product-orientated application of transition metal compounds are expounded upon: catalytic reactions, the modes of action of
metal catalysts and reactions at coordinated organic (and
inorganic) ligands; stereochemical aspects are discussed.
It is not possible to say that this volume is indispensable,
because there are many excellent monographs which cover
some of the topics discussed. However, because of the
choice of the contributions, their quality, and the growing
interdisciplinary importance of the material, this work will
be an enrichment for every chemical library and an invaluable aid for many chemists.
Giambattista Consiglio
Technisch-chemisches Laboratorium der ETH Zurich
Volume 9
The ninth, last and thickest volume (1570 pages) of the
series is intended to make the information in the other
eight volumes easily available on the basis of several
search criteria. The user has the choice of five indexes for
this purpose: Subject Index (440 pages), Formula Index
(382 pages), Author Index (386 pages), Index of Structures
Determined by Diffraction Methods (3 12 pages), Index of
Review Articles and Specialist Texts on Organometallic
Chemistry (50 pages).
The Subject Index encompasses 30000 key-words, the
Formula Index more than 32000 typical compounds with
at least one metal-carbon bond (0or n; classified according to a modified Hill system). The Author Index contains
more than 30000 names from about 40000 literature references. The two following indexes can be used independently of the main work and constitute a useful addition.
Thus, the Structure Index compiled by M . I . Bruce (University of Adelaide) is a guide to thousands of organometallic structures elucidated during the period from 1927 to
1981 by X-ray, neutron or electron diffraction. Finally, interdisciplinary interest is excited by the presentation of a
multifaceted collection of secondary and tertiary literature
(G. B. Young, Imperial College of Science and Technology, University of London) covering all aspects of the chemistry of organometallic compounds.
All in all the chemist who works in university or in industry, or who sits at an editor’s desk has had placed in his
hands an extremely useful (yet very expensive and “unelectronic”) tool.
Otto Smrekar
Angewandte Chemie, Weinheim
Experimental Methods in Photochemistry and Photophysics.
By J. F. Rabek. John Wiley, Chichester 1982, 2 Volumes
together 1098 pp., bound, L 89.95
This book made a good impression on me at first glance.
The many illustrations awoke the expectation that here a
really versatile and experienced experimentalist had written something useful for experimental work in photochemistry and photophysics. Closer inspection quickly revealed,
however, that the author is by no means an experienced
experimentalist, but that, following a doubtful plan, he has
made a book out of a heterogeneous literature collection.
The aims of this book and the way in which it has been
made are set out by the author in the preface: “. ..This
book is an up-to-date survey of the majority of available
methods and commercially available equipment applied in
the study of photochemical and photophysical reactions.
Each major topic is introduced separately and is self-contained. ... The material collected in this book has been prepared from hundreds of books, papers, catalogues and private information from laboratories round the world and
from my own twenty years experience in experimental
work in the photochemistry of polymers. My task was limited to the selection and arrangement of respective information to assist scientists, people from industry and students working in the field of experimental photochemistry
and photophysics ...”.
The sources of the material in the book can actually be
identified as (1) catalogues, (2) books and (3) journals, because the source of each figure or table is usually (but not
always) cited. The book also contains material that (4) cannot be traced to a single source or ( 5 ) does not refer to experimental methods.
(1) Catalogs: Here the author is, de facto, advertising
for particular manufacturers. He does not shrink from using their texts as well as their illustrations and tables. Examples : Chapter 4, “Optical Systems”, is largely identical
with the catalog “Optics Guide” issued by the Melles
Griot company, and Chapter 12.2.2, “Photomultiplier
Tubes”, is, to a large extent, identical with the catalog of
the same name issued by the Hamamatsu company. The
fact that there are also competing companies, here, for instance, Oriel, RCA and EMI, goes unmentioned.
(2) Books: Here the author seems to have inhibitions
about reproducing texts without alterations. If he has
nothing to add himself then he alters about every other
sentence slightly, whereby the text is sometimes weakened
or even falsified. Example: Chapter, “Potassium
Ferrioxalate Actinometer”, is, essentially, identical with
chapter 7-4B-2 of the book “Photochemistry” by Culvert
and Pitts. The names Parker and Hatchard are not mentioned in this book (names are not mentioned in the text,
on principle) and of the two investigations cited in the original, the author cites only the first. The original sentence
“The solid can be stored in the dark for long periods of
time without change” has been altered in “the reagent can
be stored in a dark bottle for long periods of time.” The
original sentence “Parker and Hatchard recommended
that ... a standard calibration graph .. . be prepared” has
been altered in “for the preparation of a calibration graph
... it is necessary to prepare a standard calibration
(3) Journals: Here the author usually limits himself to
reproducing figures and tables with a few lines of text as
commentary. Example: Chapter 19.3.3, “Frequency Mixing Technique (Part II)”, reports on two publications, [l]
“Generation of Vacuum Ultraviolet Radiation in PhaseMatched Cd Vapor”, A. H. Kung et al., Phys. Rev. Lett. 29
(1972) 985, and [2] “Tunable Coherent Vacuum-Ultraviolet
Generation in Atomic Vapors”, R. T. Hodgson et al., ibid.
32 (1973) 343. What has Rabek made out of these publications? The commentary is only 12 lines long. The physical
basis of the method is not explained. Fig. 1 is taken from
both [l] and [2] and altered without specific mention. The
reader is left to assume that these are the original figures.
The alteration in Fig. 1 of 111 has resulted in the loss of the
important words “heat pipe oven” and the vacuum UV detection part. In Fig. 1 from [2] part of the block diagram of
Angew. Chem. Int. Ed. Engl. 22 (1983) No. I0
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