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Book Review Coordination Compounds en gros and en dtail Comprehensive Coordination Chemistry. The Synthesis Reactions Properties and Applications of Coordination Compounds. (In 7 volumes). Edited by G. Wilkinson R. Gillard and J. A

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ions, here on a partly positive boron atom - by C- Si hyperconjugation (resonance formulas C, C‘).“ 31
We consider the C-Si hyperconjugation to be the main
reason for the B-C double bond in 6b being very short in
spite of weaker n-bonding (resonance formula A).[’51The
electronic stabilization of the B -C double bond by the silyl
groups might also contribute to the easy formation of 4 and
6. In addition, the steric requirements of the silyl substituents
contribute decisively to the kinetic stability of these methyleneboranes.
Received: January 27, 1989;
revised: March 16. 1989 [Z 3144 IE]
German version: Angebr. Chem. 101 (1989) 761
CAS Registry numbers:
l a , 114958-96-2; 1 b, 120637-66-3; 2a, 120638-15-5; Zb, 120638-19-9; 3a,
120638-16-6: 3b, 120638-20-2; 4a, 120638-17-7; 4b, 120638-21-3; 6a, 12063818-8; 6b, 120638-22-4; 8, 120638-23-5: Me,SnC1,1066-45-1.
[l] R. Hunold, M. Pilz, J. Allwohn. M. Stadler, W. Massa, A . Berndt, Angeir.
Chem. 101 (1989) 759; Angen. Chem. lnr. Ed. Engl. 28 (1989) 781.
[2] Previously there were indications of the reverse reaction path, i.e. the
[2 +2]-cycloaddition of methyleneboranes to give 1,3-diboretanes: B.
Glaser. E. Hanecker, H. Noth, Chem. Ber. 120 (1987) 659.
[3] Color test for methyleneboranes, cf. H . Lukasch, G. Schmidt-Lukasch, U.
Lippold, A. Berndt, Angew. Chem. 100 (1988) 959; Angew. Chem. In/. Ed.
Engl. 27 (1988) 960. The color test fails in the case of 6a, b, apparently for
steric reasons.
[4] 3b: X-ray structure analysis: C,,H,,B,Si,,
space group P i . Z = 2,
a = 981.3(9), h = 1313.8(9), c = 1357.4(10) pm; m = 64.17(8). p =
85.53(5), y = 81.16(6)’; 2994 unique reflections with Fo > 30(F0) measured on a four-circle diffractometer (CAD4, Enraf-Nonius) with Cu,,
radiation at -80°C; n o absorption correction ( p = 10.5 cm-I). H atoms
were refined groupwise with common isotropic temperature factors. The
methyl groups on Si were assumed to be rigid groups. Anisotropic temperature factors were used for all other atoms. 446 parameters, R = 0.067,
W R= 0.058 (M.= l/uz(FJ). Further details ofthecrystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik. Mathematik GmbH, 0-7514 Eggenstein-Leopoldshafen 2
(FRG), on quoting the depository number CSD-53 833. the names of the
authors, and the journal citation.
[5] P. von R. Schleyer, D. Kost, J Am. Chem. SOC.110 (19x8) 2105, and
references cited therein.
[6] I n the methyleneboranes 4, 6 and 7 the C atoms that are bound to the
dicoordinated B atoms are shielded by ca. A6 = 20 compared to comparable C atoms bound to tricoordinated B atoms. Similar shieldings are observed for C atoms on dicoordinated C atoms of alkynes. NGrh has drawn
attention to the corresponding shielding in an amido(methy1)boron cation
and in benzoyl and thiobenzoyl cations: H. Noth, U.Staudigl, H. W.
Wagner, Inurg. Chem. 21 (1982) 706.
171 G. Fritz, W. Himmel, Z. Anorg. Allg. Chetn. 448 (1979) 55.
[a] G. Boche, H. Etrrodt, M. Marsch, W. Thiel, Angeu.. Chem. 94 (1982) 141;
Angebr. Chem. Inf. Ed. Engl. 21 (1982) 132; A n g w . Chem. Suppl. 1982,345.
and references cited therein.
191 B. T. Luke, J. A. Pople, M. B. Krogh-Jespersen, Y Apeloig, M. Karni, J.
Chandrasekhar, P. von R. Schleyer, J Am. Chem. Soc. 108 (1986) 270.
[lo] G. Frenking. H. F. Schaefer 111, Chem. Ph.vs. Lerr. 109 (1984) 521.
[I 11 Concerning the extent of stabilization of carbanions by a-silyl substituents
see: D. M Wetzel, J. I. Braumen. J. Am. Chem. SOC.110 (1988) 8333; for
interpretation: P. von R. Schleyer, T. Cidrk, A. J. Kos, G. W. Spitznagel, C.
Rohde, D. Arad, K. N. Houk, N. G. Uondan, ibid. 106 (1984) 6467.
[I21 For the stabilization of vinyl cations isoelectronic with methyleneboranes
by p-silyl suhstituents see: S. G. Wierschke, J. Chandrasekhar, W. L. Jorgensen, J Am. Chem. SUC.107 (1985) 1496.
[13] The geometric requirements for C-Si hyperconjugation [14] are optimal
in bis(sily1)methyleneboranes such as 4 and 6 since an empty p-orbital on
the boron lies in the plane of the C-Si o-bonds. Furthermore, greater
overlap is facilitated by the short B = C distance. The IS-x interaction is
energetically favored by the positivization of the boron atom. i.e. the
Increase in its electronegativity (lowering of the LUMOs).
1141 Cf., e.g. : I. Fleming: Grenrorbirale und Reaktiunen organi.scher Verbindungen, Veriag Chemie. Weinheim 1979, pp. 96-97.
[15] For bond shortening by hyperconjugation see also A. Hofner, B. Ziegler,
W. Massa. A. Berndt, Angew. Chem. 10f (1989) 188; Angen. Chem. I n r . Ed.
Engl. 28 (1989) 186, and references cited therein.
BOOK REVIEWS
Volume 1: Theory and Background
Coordination Compounds
en gros and en dktail
Comprehensive Coordination Chemistry. The Synthesis, Reactions, Properties and Applications of Coordination Compounds. (In 7 volumes). Edited by G. Wilkinson, R . Gillard
and J. A . McCleverty. Pergamon Press, Oxford 1987.
Approx. 7000 pp. in total, hard cover, $2450.00. ISBN 0-08-026232-5
786
$3 VCH
Veriag.sgesell.~chuft
mhH. 0-6940 Weinheim, 1989
A total of 18 authors have here set themselves the task of
compiling the introductory volume of this new work of reference. Its 17 chapters aim to provide the intending user of
“Comprehensive Coordination Chemistry” with a summary
of those general aspects of chemistry that are relevant to
coordination compounds. The volume concludes with a subject index and a formula index.
The chapters that have been chosen for inclusion in this
introductory volume can be divided into several subject
groups. Chapters 1.I and 1.2 are historical reviews of the
development of coordination chemistry. The period up to
1930 is dealt with by G. B. Kauffman, who is well known for
his reviews and essays on this subject, while the period from
1930 on is covered by an outstanding coordination chemist,
.
I
C. Bailar, Jr., who has himself made important contributions to the development of the field. These two introductory
chapters undoubtedly provide useful background knowledge
on this segment of inorganic chemistry, though Chapter 1.2
can highlight only the most important trends and insights.
The custom of starting a major collected work with the historical development of the field of study, describing not only
0570-0833jX9j0606-0786 S 02.SOiO
A n g w . Chem. Int. Ed. Engl. 28 (1989) Nu. 6
its chronology but also the scientists involved and their individual contributions, is one that is worth preserving. Other
chapters too in this volume are very impressive. D.L.
Kepert’s treatment of coordination numbers and geometries
(Chapter 2), in which complexes with coordination numbers
from 5 to 12 are discussed on the basis of the VSEPR principle, is detailed, sound and well illustrated with figures, its
only omission being the absence of alternative descriptions
of coordination polyhedra and their polytopic rearrangements (e.g. those based on quantum mechanics). Chapter 3 is
a lesson by 7: B. Shun on the nomenclature of coordination
compounds; the necessity for this and the content of the
article are beyond question. In Chapter 4 I. G. Dunce provides a very useful classification of metal cluster compounds
and clathrates in list form (with clear structural formulas
which are a welcome aid to the reader). As is always the case
with undertakings of this sort, the question arises here (as
also in other chapters) of how up-to-date the information
can be made. Published work up to 1983 is taken into account, but quite a lot has happened in the field of clusters in
the intervening years. A few of the sections in this chapter,
such as those on bonding (where only clusters of the cubane
type are covered), o r on synthetic methods (one and a half
pages of text), are too rudimentary. In Chapter 5, on isomerism in coordination complexes, the ground covered by J. M .
Harrovilfield and S. B. Wild is essentially the same as is usually treated in inorganic chemistry textbooks o r elementary
lecture courses o n complex chemistry, apart from unnecessarily introducing the newly coined words “allogonism” and
“allogone” in connection with geometrical isomers, failing
to mention the “bond-stretch’ isomerism whose existence
was recently established, and the inclusion of some material
which overlaps with that in Chapter 2. Ligand field theory
and its modifications, and the “angular overlap” model,
which are treated in Chapter 6 (B. N . Figgis), are undoubtedly an important part of the theoretical background of coordination chemistry, but after looking through this chapter one
is left with doubts about its usefulness. These topics are
treated in several excellent and considerably more detailed
monographs and textbooks (not least those by the same author). Many of the points are merely touched on briefly (e.g.
“Excited States and Photochemistry” is given only one and
a half lines of text with four literature references), and the
omission of other electronic structural theories of coordina-.
tion compounds from this chapter, the only one devoted to
bonding theory, gives a somewhat unbalanced picture of the
quantum chemistry of inorganic complexes.
A further five chapters deal with the general theme “Reaction Mechanisms”. Chapters 7.1 on substitutions ( M . L.
Tobe), 7.2 on electron transfer reactions (7: J. Me-yer and H .
Tauhe), and 7.3 o n photochemical processes (C. Kutal anti
A . W. Adamson), are all written by authors whose names are
inseparable from the respective chapter titles. They are impressive, especially that which has the doyen of this subject.,
Tauhe, as one of its authors. The treatment of photochemical
processes includes more than 200 literature references; newcomers to the research topic will note this with considerable
satisfaction, as there is scarcely one useful monograph on
this topic, and even less in the way of textbooks. Chapter 4,
in which D. St. C. Black fills the greater part of the 44 pages
with formula schemes, mainly describing the reactions of
metal-bonded chelate ligands, is followed by a short chapter
by H . E. LeMuy, Jr. on solid state reactions of coordination
compounds, which reveals how little knowledge exists about
this area. Next follow three very brief reviews of electrochemical aspects of coordination chemistry. Although it is
true that brevity can often be the soul of wit, it seems odd
Anjiew. Chem. Int. Ed. Engl. 28 (1989) No. 6
$3
that the first of these three chapters (with its very general
sounding title “Electrochemistry and Coordination Chemistry”) by C. J. Pickett contains only material which could
easily have been integrated into the two following chapters
(by D. H . Vuughun and C. J. Pickett respectively). These latter two are likewise not very informative, and could have
been combined together. Following Chapter 9 by D. H.
Vaughan, from which one learns something about solvent
effects on the rates of reactions, redox potentials and equilibrium constants of coordination compounds, the final chapter by H . M . N . H. Irving reviews the important applications
of coordination compounds in analytical chemistry. This article again is mainly useful for its collection of relevant literature references, which gives the non-specialist easy access to
appropriate background reading.
The overall impression from this first volume of “Comprehensive Coordination Chemistry” is one of rather wide variations in the quality, quantity, usefulness and importance of
the individual chapters. Excellent surveys appear alongside
other chapters that could with equal benefit be replaced by
lists of relevant review articles. It would perhaps be not such
an outrageous idea if multi-volume works of this sort were to
have, instead of a whole volume devoted to “Theory and
Background”, just one chapter covering as many as possible
of the most up-to-date relevant reviews and monographs,
even though the saving of one volume would probably not
lead to a significant reduction in the price of the whole set.
Peter Hofmann
Anorganisch-chemisches Institut
der Technischen Universitat Miinchen, Garching (FRG)
Volume 2: Ligands
In multi-volume works it is a truism that a systematic and
well-organized treatment of the subject makes the collection
attractive, and reduces the gaps left for other authors and
publishers to fill; in practice, however, a successful recipe is
not found in every case. Comparing the present work with
“Comprehensive Organometallic Chemistry”‘*’ it emerges
that significant progress has been made in this respect. Volume 2 (together with Vol. 6) gives probably one of the most
obvious indications of this.
In the past the attitudes of metal complex chemists and
organometallic chemists have been strongly metal-orientated. In contrast, there is now a trend towards thinking more
in terms of ligands. Which ligand should one choose in order
to make a complex more stable o r more labile? Which ligand
offers the best possibilities as an analytical probe? How can
molecules in the coordination sphere be switched around?
This volume directly o r indirectly answers many of these and
similar questions. For this reason the collection will become
an important standard work, not only for organometallic
chemists but also for organic chemists, biochemists and biologists. There are, of course, too many instances of overlapping in content between this and the other volumes, and this
must ultimately have an effect on the total price of the work.
However, the volume on “Ligands” is so useful that such a
consideration will not prevent it being bought.
The ligands are grouped according to the obvious classification based on donor atoms. Thus there are eight chapters
on nitrogen-containing ligands, one on ligands containing
elements of Main Group 5, with the greatest emphasis on
phosphorus, nine on oxygen-containing ligands, six on sul
fur-containing ligands, and one each on ligands in which the
[*I
Cf. Angew. Chem. 95 (1983) 819; Angew. Chem. Inl. Ed. En,ql.
22 (1983) 797.
VCH Verlugsgesekhafl m b H , 0-6940 Weinheim. (989
0570-0RU~X9~0606-o787
$02.50!0
787
donor atom is selenium, tellurium, a halogen or hydrogen. A
further eight chapters deal with ligands having two or more
different donor atoms. Especially noteworthy is the extensive treatment of macrocycles with nitrogen and oxygen donor centers (sulfur analogs of these are listed only briefly
under thioethers). Next a separate chapter is devoted to ligands of natural origin (covered only very briefly, however,
omitting alkaloids for example). Further chapters treat
cyanides and fulminates, then ligands containing silicon, germanium, tin and lead, and lastly mercury as a ligand; however, the analogous copper ligands and the gold ligands which
have been particularly thoroughly studied are unaccountably omitted.
In more than a thousand pages many well-known experts
have here applied their best efforts to bringing order to this
many-faceted subject. The result stands up to scrutiny; it is
a mine of information for all chemists, from the student to
the committed researcher or the industrial chemist. An “exhaustive” treatment is, of course, something aimed for but
never fully attained. Some readers will find that “their” ligands are not covered or are not given due attention. Those
that may be missed include the nitrido ligand, the intentionally (but unjustifiably) omitted dinitrogen, thiazyl fluoride
and thioformaldehyde ligands, and the trialkylamines, especially with regard to their interaction with alkali metal ions.
Many of the chapters contain useful directions concerning
nomenclature. Regrettably, though, hardly any of the chapters give an indication of the date up to which the literature
has been scanned.
Unfortunately the editors have missed an important opportunity by failing to impose uniformity in the manner
whereby the properties and bonding capabilities of the ligands are presented and discussed; this would have made
comparisons easier, an important matter from the reader’s
standpoint. The only chapter sub-sections in which this has
been done are 13.2 to 13.4 (N-donor ligands), 15.2 (on the
ligands O,, OF and O:”), 16.1 to 16.3 (S-donor ligands) and
19 (hydrogen and hydrides); the discussion on the bonding
of ligands containing phosphorus and its homologs is especially worth mentioning. In many of the articles the authors
have been content to include sub-sections with titles such as
“Properties”, “Structure”, “Spectroscopic Data” or “Types
of Coordination”. However, to describe the ligands the authors use many different concepts or terms: the coordination
number, “soft” or “hard”, a good or poor donor or acceptor, the position in the spectroscopic series; information on
isoelectronic ligands is occasionally given. The energies of
the HOMOS or LUMOs are missing, as are their relative
sizes.
At the end of the volume there is a subject index (37 pages)
and a formula index (75 pages). Unfortunately the latter is
only arranged according to the metal atoms, with the result
that a ligand can be located from its empirical formula only
with difficulty.
Frank H . Kohler
Anorganisch-chemisches Institut
der Technischen Universitat Miinchen, Garching (FRG)
Volume 3: Main Group and Early Transition Elements
Volume 3, with 25 chapters consisting of 1400 pages, describes the coordination chemistry of the Main Group elements and the “early transition elements”. The article on the
coordination chemistry of phosphorus could not be completed in time, and will appear later in the journal Polyhedron
(note also “Technetium” in Volume 4). All the chapters (ex788
0 VCH
Verlagsgesellschaft mhH, 0-6940 Weinheim, 1989
cept that on molybdenum) have a similar construction, being
arranged according to the various ligands for a given central
atom. This results in a consistency within the volume which
is by no means always found in multi-author reference works
of this type. Organometallic/metalloid compounds have deliberately been excluded, with very few exceptions, a fact
which is not immediately apparent from the title of the reference work, but is explained in the preface. Readers are there
referred to the sister series “Comprehensive Organometallic
Chemistry” for this class of compounds.
The first 300 pages are devoted to the coordination chemistry of the Main Group elements. The contribution by D.E.
Fenton on the coordination behavior of the alkali and alkaline earth metals (70 pp., with 598 references extending up to
2985) has turned out very successfully, with the main emphasis, as expected, on the complexation of these metals with
polydentate and macrocyclic ligands (crown ethers,
cryptates, porphyrins etc.). The resulting structures are
shown very clearly, either schematically or as pictorial
molecular diagrams. This feature proves especially useful in
the final section of the chapter (IOpp.), which deals with
naturally occurring ionophores as ligands. The currently
topical question of what factors influence the selectivity and
the stability of the complexes is discussed in detail.
The chapter on the coordination chemistry of boron by J.
Emri and B. Gyiiri (20 pp., 172 references extending up to
1984) treats the complexes, classified according to ligands, in
text linked to tables, each with a separate bibliography; thus
the reader has no difficulty in quickly finding the required
reference. This useful arrangement is also found in the other
chapters.
The following chapters by M . J. Taylor on the coordination chemistry of aluminum and gallium (37 pp., 690 references up to 1985) and by D.G. Tuck dealing with indium and
thallium (22 pp., 438 references up to 1983) are packed with
much information; however, as might be guessed from the
small numbers of pages, the form of presentation is less
user-friendly in this case. Complicated structures are merely
described rather than drawn, and the reader is hurried from
one heading to the next.
The chapter by P . G . Harrison on the coordination chemistry of silicon, germanium, tin and lead (40 pp., 663 references up to 1985) reviews a considerable amount of wellestablished knowledge, but also includes a more topical section on “Multiple Bonding Involving Silicon, Germanium
and Tin”. Thus the chapter does not completely exclude the
occurrence of carbon itself as a “ligand”. Several pages are
also devoted to the cyclopentadiene ligand and to the related
carbaboranes. The presentation as a whole lacks clarity, and
cannot be said to be satisfactory. Moreover, many aspects of
the chemistry of these elements cannot be regarded as “coordination chemistry” without straining the definition.
The chapter by C. A . McAulyfe on the coordination
chemistry of arsenic, antimony and bismuth consists of 56
pages, and reviews 272 publications (extending up to 1985) in
a clear comprehensible style. The three elements are treated
separately. Although this procedure facilitates searching for
specific compounds, comparisons within the triad of elements, which can often be very useful, are thereby made
more difficult; in a “parallel” method of treatment such
comparisons emerge naturally. However, the easy style
makes refreshing reading, and valuable glimpses of matters
of current controversy are included.
The appropriately brief chapters on the coordination
chemistry of sulfur, selenium, tellurium and polonium (F. .
I
Berry, 8 pp., 85 references up to 1983), and of the halogens
and inert gases ( A . J. Edwards, 10 pp., 102 references up to
0570-0833j89/0606-0788$02.5010
Angew. Chem. hi.Ed. Engl. 28 (1989) No 6
1984), are followed by chapters on the “Early Transition
Metals” (i.e. titanium to chromium, the lanthanides and the
actinides). A separate chapter is devoted to the iso- and
heteropolyanions ( M . T. Pope, 25 pp., 140 references up to
1985). The coordination chemistry of molybdenum is covered in six chapters, written respectively by A . G. Sykes,
G. L. Leigh, R. L. Richards, C. D. Garner, J. M . Charnock
and E. I. Stiefel. These molybdenum chapters have been
placed at the end for reasons of timing, and are preceded by
the chapters on titanium (C. A . McAuliffe and D. S. Baratt),
zirconium and hafnium ( R . C. Fay), vanadium ( L . F: Vilas
Boas and J. Costa Pessoa), niobium and tantalum ( L . G.
Hubert-Pfalzgraf, M . Postel and .
I
G. Riess), chromium
( L . E Larkworthy, K. B. Nolan and P. O’Brien),tungsten ( Z .
Dori), the lanthanides (F: A. Hart) and the actinides ( K . k%
Bagnalf). All the chapters are competently written, and they
will be useful to a wide readership. In contrast the preceding
300 pages on the coordination chemistry of the Main Group
elements are out of place in this volume.
Hubert Schmidbaur
Anorganisch-chemisches Institut
der Technischen Universitat Munchen, Garching (FRG)
Volume 4: Middle Transition Elements
Having already introduced the semantically questionable
terms “early” and “late” to classify the transition elements,
this bad practice is now continued in Volume 4 of the work
with the so-called “middle transition elements”. These comprise the elements of the manganese, iron and cobalt groups
of the Periodic Table. The coordination chemistry of these
elements - with the exception of the article on technetium,
which was not ready in time and will appear later in the
journal Polyhedron -is described in 1400 pages, the contributions being of a consistently high quality. The chapter on
manganese (by B. Chiswell, E. D. McKenzie and L. E Lindoy) is quite extensive, well organized and reasonably comprehensive; the only area dealt with too briefly is that of
manganese compounds with coordination numbers of five to
seven. Another pleasing contribution to this volume is the
carefully prepared account of the inorganic chemistry of rhenium, which is skilfully organized according to Iigands and
structural units. However, the treatment in this chapter of
the higher valency hydrides especially seems unsatisfactory
with regard to completeness and presentation ; the applications of this class of compounds in the chemistry of “CH
activation” ought to have been included (e.g. the work of
Felkin). The chapter on rhenium ( K . A. Conner and R. A.
Walton)is a valuable mine of information for all whose work
involves this element, or who would like to make a start in
rhenium chemistry. The two chapters on iron also are clearly
structured, under the heading of Fe(I1) complexes and lower
oxidation states (P. N . Hawker and M . Y Twigg) and that of
Fe(II1) compounds and higher oxidation states (S. M . Nelson). However, these chapters lack detailed descriptions of
biologically relevant systems with an adequate coverage of
the literature, and also references to modern developments in
organo-iron chemistry. For the contribution on osmium the
editors have found in W P. Grif$th an especially competent
and expert author. This chapter, clearly set out according to
ligands, with sub-divisions for the different oxidation states
of osmium, is a really excellent resource for researchers engaged in osmium chemistry. The expert selection and presentation of the structural chemistry details here deserves a special mention. The author also gives a correct and historically
aware account of the development of the osmium tetraoxide
Angcw. Chrm. Int.
Ed. EngI. 28 (1989) No. 6
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catalyzed olefin oxidation process (cis-hydroxylation,
p. 590 ff.). The elements cobalt (D.A . Buckingham and C. R.
Clark) and rhodium (I/: H. Jardine and P. S. Sheridan) receive the most extensive and detailed treatment (altogether
460 pages and 2500 references). The Wilkinson complexes of
the CIRh(PR,), type are deservedly given the most detailed
treatment including tables. In the chapter on iridium ( N .
Serpone and M . A. Jamieson), with its sometimes badly proportioned pictorial formulas (e.g. on pages 1102, 1105, 11 12,
11 15 and 3 151), a pleasing feature is the account of the catalytic activity of this element (see the tables on page 1159);
although short, it includes a very useful compilation of key
references.
Wolfgang A . Herrmann
Anorganisch-chemisches Institut
der Technischen Universitat Munchen, Garching (FRG)
Volume 5: Late Transition Elements
This volume contains chapters on the coordination chemistry of the nickel, copper and zinc triads of the Periodic
Table. It begins with an excellent survey of the coordination
chemistry of nickel by L. Sacconi, F: Mani and A. Bencini. In
this, the longest of the chapters with about 350 pages, more
than 3200 publications are competently reviewed. In a few
instances literature published up to 1985 is included, but in
general the coverage extends up to 1984. The material is
arranged primarily according to increasing nickel oxidation
states, then further divided according to Iigands. An especially commendable and useful feature is the clear way in
which the different ligand systems are presented, as also are
the many tabulations of physical-chemical data and the enumeration of related ligand systems. It is only by these means
that an adequate coverage of the large variety of ligdnds can
be given. In this and the following chapters important molecular structures are reproduced directly from the original papers, in contrast to the practices usually followed in tertiary
publications of this sort. In addition stereochemical diagrams are used in important cases to make intermolecular
interactions clearer to the reader. This form of representation is a welcome aid, as it helps one to understand threedimensional molecular relationships.
D. M . Roundhill, in his chapter on the coordination chemistry of platinum, with 182 pages of text and about 2000
literature references, adopts a quite different arrangement of
the material. Here the system is based on the ligands, ordered
according to the position of the donor atom in the Periodic
Table-a method of classification which does not always
make for clarity of presentation.
In the account of the coordination chemistry of copper by
B. J. Hathaway, which is quite a lengthy one with 250 pages,
the spatial relationships of the many cluster compounds included are in some cases not shown very effectively. The
coordination chemistry of silver (R. J. Lancashire) is treated
in a less comprehensive fashion, with only 500 literature
references.
R. J. Puddephatt’s contribution on the coordination chemistry of gold illustrates that much advantage can be gained
by having articles on related topics written by the same author, even though the aims may be different. Although some
overlapping is almost inevitable in works of this scale, such
an arrangement would have considerably reduced the duplication between articles in this series and others in the sister
series “Comprehensive Organometallic Chemistry”,
The article on zinc and cadmium (122 pp., 1470 references) by R. H . Prince includes detaiIed sections devoted to
Vcrlugspsell::chufi mbH. D-6940 Weinheim, 1989
0570-o833/N9/06(~6-o7RY
$02.50/0
789
industrial applications and to biological aspects of these elements, which are very useful. Although these important
facets are also touched on in the chapter on copper, they are
absent or less clearly stated in the rest of the chapters. The
account by K . Brodersen and H . U. Hztmrnel of the coordination chemistry of mercury (1 24 pp., 600 references) follows
very conventional lines in the choice of material, indicating
an outlook which has now almost disappeared from the German literature. Even the introduction strikes one as awkward and constrained.
To conclude these comments, the articles on the coordination chemistry of palladium by C. E J. Barnard and M . J. H .
Russell, and by A . 7: Hutton and C. P. Morley, both much
too brief, with altogether only 660 literature references (only
a few of which are more recent than 1980), give a rather
inadequate account of the current state of knowledge in this
field. Applications, such as those to catalysis, are not discussed at all. These chapters are definite weaknesses of the
volume, and the reader would be well advised to refer also to
the complementary volume of “Comprehensive Organometallic Chemistry” (see footnote on p. 787) for additional
information.
Carl Kriiger
Max-Planck-Institut fur Kohlenforschung
Mulheim a. d. Ruhr (FRG)
chemistry and in reducing toxic smoke emission from burning of PVC.
Despite the fact that the literature coverage is not always
ideal, this is on the whole a well-written and very clearly
presented volume, and reading through it or merely browsing will reveal plenty of new ideas, and perhaps surprises,
whether the reader’s interests lie in basic research or in applications. This useful volume should find a place in every
library, as an aid both to those starting in a new field and to
others wishing to round off their knowledge.
Heinz P. Fritz
Anorganisch-chemisches Institut
der Technischen Universitat Munchen, Garching (FRG)
Volume 7: Indexes
The formula and subject indexes for Volumes 1 to 6 are
collected together in this volume. It also includes a list of
review articles relevant to this subject area.
[NB 920 IE]
Metal-Ligand Multiple Bonds. By W. A . Nugent and J. M .
Mayer. Wiley, Chichester/New York 1988. xi, 334 pp.,
hardcover, E 35.151s 55.00. -ISBN 0-471-85440-9
Volume 6: Applications
In the 16 chapters of this volume, experts from universities
and industry describe the applications and importance of
coordination chemistry in a wide variety of currently topical
fields. It is no surprise to find that the publications cited
show a bias towards those in the English language. On the
other hand it is regrettable in a work published in 1987 that,
whereas the important and lengthy chapter by M . N . Hughes
cites papers as recent as 1986, in others, such as those on
“Dyes and Pigments” (Chapter 58) and on “Applications in
Photography” (Chapter 59), the most recent citations are to
1983 papers (and even these are only patents or patent applications). As a result the usefulness of these parts of Volume 6
as reports on the “current” situation in applied research is
considerably reduced. This turns out to be the case for all the
areas that are undergoing rapid development, e.g. in “Electrochemical Applications” (Chapter 57), and in “Compounds with Novel Electrical Properties” (Chapter 60), although it is true that there are as yet few actual applications
in the form of fully developed systems.
Chapter 61 consists of five sections: “Stoichiometric Reactions of Coordinated Ligands”, “Catalytic Activation of
Small Molecules” (which in particular describes hydrogenations, hydroformylations and carbonylations, classified according to the metals involved), “Metal Complexes in Oxidation Reactions”, “Lewis Acid Catalysis in Reactions of
Coordinated Ligands”, and “Decomposition of Water into
its Elements”.
The treatment of biological and medical aspects in Chapter 62.1 (the longest) is detailed and pleasingly up-to-date, as
are those on the applications of coordination compounds in
chemotherapy (Chapter 62.2) and in radiopharmacology
(Chapter 65).
Geochemical aspects and prebiotic systems are discussed
in Chapter 64. The articles on “Metal Extraction” (hydrometallurgy) (Chapter 63) and on “Nuclear Fuel Cycles”
(Chapter 65) describe well-established technological applications. Finally Chapter 66 summarizes miscellaneous applications, ranging from hydrogen storage to uses in agricultural
790
6
VCH Verlugsgesellschajt mhH. 0-6940 Weinheim, i989
This superb book by W. A . Nugent and J. A . Mayer on
metal -1igand multiple bonds provides a thorough review on
the chemistry of transition-metal complexes with M -0,
M-N, and M-C multiple bonds. This is the first time that
these related types of complexes have been treated together
comprehensively and compared with one another.
The seven chapters describe the electronic and geometric
structures, the synthesis and spectroscopic properties, and
the reactivity and catalytic activity of these complexes. The
first chapter introduces the different types of complexes: 0x0
complexes, nitrido, imido, and hydrazido complexes, and
different compounds with M - C multiple bonds, including
Fischer- and Schrock-type carbene complexes as well as carbyne complexes. Unfortunately, complexes in which the metal exhibits multiple bonds to main-group elements other
than 0, N, and C are not discussed, although these complexes are equally interesting and a focus of current attention.
Inclusion of these complexes would have allowed more extensive comparisons. Presumably, however, this would also
have led to an unwieldy text. In the second chapter, the
bonding and electronic structure of these complexes are discussed. The following two chapters provide a detailed description of the currently available routes to compounds
with metal-ligand multiple bonds and a summary of their
vibrational and NMR spectra. The 0, N, and C NMR resonances are discussed extensively. Chapter five offers a comprehensive review of the crystal structures and, in particular,
the M - 0 , M-N, and M-C bond lengths. Chapters six and
seven thoroughly treat the reactivity of metal -1igand multiple bonds and their role in catalysis.
This book is a gold mine for all chemists interested in the
area of metal -1igand multiple bonds or requiring specific
information on such complexes. Especially valuable is the
exhaustive literature survey, including publications appearing in 1987, which may be rapidly scanned and helps the
reader in finding answers to specific questions. The book is
excellent as a basic text for advanced study in courses and
seminars. Despite the cutbacks in library budgets, which
have placed severe limitations on the purchase of new mono-
0570-08331RSj0606-0790 S 02 SO10
Angew. Ckem. Int. Ed. Engl. 28 (1989) N o . 6
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