June 5, 1959
BOOKREVIEWS
2915
The interest in the observation we report is not so much that 2,2'-bipyridine so markedly inDEPARTMENT OF CHEMISTRY LEONH. ZALKOW creases the reactivity of Cr++ for C0("3)6+++, WAYNESTATEUNIVERSITY F. X. MARKLEY but rather that i t opens up the possibility of studyCARLD JERASSI DETROIT2, MICHIGAN ing the reduction of the large class of Co(II1) RECEIVED APRIL9, 1959 complexes by a reagent which acts retaining an intact coordination sphere. Considerable work with Cr++aq., which with all Co(II1) complexes T H E OUTER SPHERE ACTIVATED COMPLEX IN T H E 6studied except Co(NH3)aff+and perhaps Co("3) REDUCTION OF Co(1II) SPECIES' OHz+++ makes use of a bridged activated complex, Sir : has already been done. Thus a systematic study In much of the work done on oxidation-reduction can be made of the influence on the rate by each of reactions of Cr(II), the role of the bridged activated the distinct mechanisms of changing the composicomplex has been e m p h a ~ i z e d . I~n ~particular, ~ ~ ~ ~ ~ tion of the oxidizing agents; furthermore the chemiwhen Co(II1) or Cr(II1) complexes are oxidizing cal and isotopic effects characteristic of each type agents, proof has been adduced that the reactions of mechanism can now be assessed. I t perhaps proceed through activated complexes in which there needs to be emphasized that Co(II1) complexes is interpenetration of coordination spheres. We qualify especially for these studies because they now report the results of experiments using a com- undergo substitution slowly. plex of Cr(I1) which reacts by means of activated It is interesting to note that even when a bridged complexes in which there is no interpenetration in activated complex is not involved, Co(SH3)5the same sense. OHZ+++ reacts with a reducing agent much more The reaction of Cr++aq. with CO("3)6+++ rapidly than does CO("3)6+++, and the rate is slow2 and the specific rate a t 25' a t p = 0.41 ratio using Cr(dip)B++is cn. 90. On changing the (Cl- as the anion) has now been measured as solvent from HzO to D20, the rate a t which Co0.16 ni.-l min.-l. However, when Cr++aq. (NH3)6+++ reacts with Cr(dip),++ is reduced by is converted to Cr(dip)3++ (dip = 2,2' bipyridine), less than lo%, but a slight decrease, ca. 30%, is the rate of the reaction is much increased. Thus noted when Co(NH3)6+++ is used as oxidant. a t p = 0.20 (NaC1) and 2 5 O , the specific rate of However, when Co(NH3)50D2+++ reacts in D20 the reaction between Cr(dip)3++and Co(NH&+++ the rate is decreased by a factor of ca. 2.5 from the The rate is independent rate for Co(NH3)50Hz+++ in HzO (this rate ratio is 1.5 X l o 4 m.-I min.-'. of the concentration of 2,2' pyridine as long as a can be compared to the decrease of 3.9 observeda sufficient excess is present, and it is independent of in making a similar comparison with Cr++aq. as p H over a considerable range, 5.5 to 3.5. It has reductant). A striking difference between the two been shown that 3 bipyridine groups are associated kinds of mechanisms is in the sensitivity to the with each Cr++ under these conditions, and that change from Co(NH3),0H2+++ to C O ( N H ~ ) ~ O H + + . the chromium product is Cr(dip)a+++. At low This change occasions an increase in specific rate pH, the rate of the reaction increases, presumably by a factor of ca. lo' when Cr++aq. is the reducbecause Cr(dip)++ or Cr(dip),++ reacts with tant,6 but by less than 100, and perhaps by as CO("B)B+++ even more rapidly than does Cr- little as 10, when C r ( d i ~ ) ~reacts. ++ (dip)3++. Chemical Co., St. Louis, Mo., for a supply of the starting ketone IV.
(1) This work is supported by the Atomic Energy Commission under Contract ffAT(ll-1)-378. (2) H. Taube and H. Myers, THISJOURNAL, 76, 2103 (1954). (3) H. Taube and E. L. King, i b i d . , 7 6 , 4053 (1954). (4) D. L. Ball and E. L. King, ibid., 8 0 , 1091 (1958). ( 5 ) A. E. Ogard and H. Taube, ibid., 80, 1084 (1958).
(6) A. Zwickel and H. Taube, ibid., 61, 1288 (1959)
GEORGEHERBERT JONES LAB. UNIVERSITY OF CHICAGO CHICAGO, ILLINOIS
A. M. ZWICKEL
H. TAUBE
RECEIVED FEBRUARY 27, 1959
BOOK REVIEWS Nouveau Trait6 de Chimie Minerlle. Tome IV. Group 11: Glucinium - Magnesium- Calcium-Strontium- Baryum Radium. PAULPASCAL,Membre de l'Institut, Professeur honorhire i la Sorbonne. Masson et Cie., 120 Boulevard Saint-Germain, Paris 6, France. 1958. xxxix 973 pp. 17 X 26 cm. Price: Broch6, 7.500 fr., cartonne toilC, 8.500 fr. The preparation of a systematic and encyclopaedic treatise on inorganic chemistry was no trifling job, seventy-five years ago; every decade t h a t has passed since then has made it a progressively more daunting enterprise. The Arcadian simplicity of Roscoe and Schorlemmer and the earliest editions of Gmelin have given place to multi-volume productions of size and price so formidable as t o restrict them almost automatically to the institutional market. T h e rwiewer is inclined to regard t h e 1908-1937 edition nf
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Abegg-Auerbach as the last comprehensive account of inorganic chemistry t h a t had some claim to readability; those skeptical of the validity of such a claim are reminded of Donnan on copper. Mellor's treatise, staggering as the single-handled labor of a sexagenarian with little more than secretarial assistance, is known to all of us as a mine of information and references on early experimental observations but it is only intermittently readable. The gallant attempt of Yost and Russell to use a portion of the Periodic Table to illustrate how a modern systematic treatise on inorganic chemistry might be written has been much and justly admired; but their effort has, alas, provoked no "envious fever of emulation." The encyclopaedic treatise is here to stay unless it is doomed to ultimate displacement by the punch-card. Since n o siich work is likelv to complete a cyrle of revisinn in lesq
than twenty-five years, it is highly desirable t h a t more understandable. The author’s boundless enthusiasm for his than one such ‘‘magnum opus” should be available, prefer- subject is evident throughout. I n large measure, this comably with publication schedules appropriately out of phase. pensates for certain interpretations with which others may The work under review is accordingly a welcome addition t o take issue and f u r occasional overly generous statements chemical libraries. Out of twenty Contemplated volumes such as the “millions of known structures with sp3 bonding” this is the fourth t o be published; it hoped to complete the ( p . 71). Quite understandably, the author’s not iiiconsiderseries by 1960 though this is perhaps unwarranted optimism. able contributions to phosphorus chemistry provide the As with Gmelin the obituary crosses in the list of collab- central themes for many of his discussions. orators are silent testimony to the truth of the ancient The text is remarkably free from mechanical errors. saying “Ars longa vita brevis.” Comparisons with Gmelin This and the over-all excellence of printing, binding and preare inevitable. “Pascal” will he a good deal shorter than sentation attest the carefulness with which the manuscript “Gmelin”; if Volume I V is typical, the individual elemelits was handled. Both author and publisher are to be comwill be covered a t lengths ranging from three quarters down 1,limented on a job well done. t o one fifth of t h a t of the corresponding treatment in the The book is strongly recommended both to those specifieighth edition of Gtnelin. The format is satisfactory and cally interested in phosphorus chemistry and to those interthe typography more pleasing than t h a t of Gmelin; on the ested in a significant contribution t o the “renaissance in other hand the French work seems less riclil5- provided with inorganic chemistry.” It is unfortunate t h a t the price is tables and diagrams. so high t h a t many individuals mill find it impossible t o acThe distant contemplation of such a formidable accuniuquire personal copies. lation of experimental fact tends t o be a trifle depressing S O Y E S CHEMICAL LABORATORY but i t is impossible t o come to close quarters with a n y UNIVERSITY OF ILLIXOIS THERALD MOELLER section of the book without encountering intriguing observations and many challenges t o further investigation. It is URBASA,II~LIXOIS probable as a source of references t h a t such works are most useful to the investigator. Here Pascal will be of great value; the deadline for references in each bibliographical Some Problems in Chemical Kinetics and Reactivity. section is clearly indicated and for some elements briiigs the T-olume I. By ? N.i SEMENOV. . Translated by MICHEL literature survey forward some twenty-five years later than BOUDART.Princeton University Press, Princeton, New the corresponding Gmelin volume. I n such cases the value Jersey. 1958. xii 239 pp. 15 X 23 cm. Price, $4.50. of Pascal as a complementary guide t o the more recent This is the second edition of a book which was published literature is self-evident. first in 1954 in a limited edition of the Academy of Sciences of the U.S.S.K. and was written in preparation for a national DEPARTMESTO F CHEMISTRY DARTMOUTH COLLEGE J. H. ~VOLFENDES symposium on Chemical Kinetics and Reactivity. After the discussions of the symposium, the author was asked to HASOVER,S . H. prepare a new edition. This was expanded to include new data from the literature and certain major additions were made to the text of the original. Two English translations, Phosphorus and its Compounds. Volume I : Chemistry. the present one by Roudart and one by Bradley for thc By JOHX R . VANWAZER,Assistant Research Director and Pergamon Press (see review below), have been authorized Senior Scientist, Inorganic Chemicals Division, :\.Ion- as well as a German edition. santo Chemical Company, St. Louis, Missouri. InterThe present volume is the first of two to be issued by the science Publishers, Inc., 250 Fifth Avenue, S e w Uork 1, Princeton Press and comprises the first two of a total of h7.Y. 1958. siii 954 pp. 15.5 X 2 3 . j cm. Price, four parts of this work. These two parts cover Radical $27.50. Reactions (reactions of chain propagation and branching) and Chain Initiation and Termination. The third and In his Preface, tlic author says “tlie purpose of this book fourth parts, on “Kinetics of Chain Reactions” are schedis t o lay the foundation for a new, separate discipline of uled to appear in Volume 11. chemistry-phosphorus chemistry.” However laudable The book was not written as a textbook or treatise, but is such a purpose may be, the creation of a new discipline that can occupy a position of equality among the classical dis- a survey, by a n outstanding scientist in the field, of developciplines of inorganic, organic, analytical and physical chem- ments in the twenty years or more since his first book on “Chain Reactions’’ was published. It emphasizes radical istry is complicated by the twin problems of ample sysand radical-chain reactions and there is a frankly personal tematization of fact and principle and of acceptance of flavor in the discussion of these. such, readers interested the body of information as sufficiently comprehensive and in chemical kinetics will find it both interesting and rewardvaried to permit continued fruitful study. By presenting phosphorus chemistry as an approach embodying many of ing. The first part of thi, volume includes an extensive disthe principles of structure and homology t h a t distinguish cussion of monoradicals and their reactivity in competitive a i l orderly organic chemistry from a n often much less orderly reactions of addition, decomposition, isomerization, or subinorganic chemistry, the author has done much t o overcomc stitution; the role of polar factors; etc. There is also a tlic first complication. By presenting :t massive, but not c~icyciopedic, array of coordinated informatioii and sug- much briefer discussion of diradicals. Reactions such as oxidation of hydrocarbons and polymerization are discussed gesting innumerable :ireas for expanding research, he has done even more to overcome the second. Whether he has in some detail. In the second part, reactions of chain h i tiation and termination :ire discussed on the h \uccerded in devising a new discipline must be determined geiieous molecular reagents, initiation by io by tlic test of time. However, it cannot be denied that effects . lie has produced a volume that will be both an outstanding This volumc has the miiior teclinical disadvautages reference for all workers in pliosphorus chemistry and :t which are to be expected in such a n edition. I t is a paper.stimulus to continuing research in this fascinating area. back edition. There are a fair number of typographical This volunie is concerned primarily with the development errors, and several instances in which limitations of type o f a set of underlying principles for phosphorus chemistrlhave resulted in rather odd notations or in the use of a arid the implementation of these principles by a thoroughly letter or symbol with more than one meaning in a single and Farefully documented body of factual information. The emphasis tliroughout is upon modern interpretation of equation or paragraph. I n :t number of instances new fuudarnental chemistry, Technology and related aspects materials have simply been appended as footnotes rather than actually incorporated into the text. of the chemistry of phosphorus are to be considered in a The author expresses a note of disappointment t h a t 8 0 subsequent companion volume. S o attempt has been made much of the extensive literature which has appeared is cont o cover every subject with absolute completeness. Rather, cerned with “disjointed observations on this or that reactile author has attempted t o examine available information tion and not with a plan of investigation from all sides.” critically and to include only t h a t which has survived his wrutiny. .4lthough some may question his judgment on He notes also that it seems to him t h a t the majority of the fundamental problems have not been completely solved as xpccific points, none can disagree t h a t his over-all selectioii yet. Xonetheless, his book does give a picture which shows is consistently good and t h a t his coverage is excellent. Phr:twology, clarity of expression and style are consider- much accomplished in building u p knowledge of a new group o f substances, such :I\ the f r w radicals represent. The abl\ ;iI)cive :iverage a i i t l rmder the. tcxt lwth readable and
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