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For rx:onple. it is possible to explain the rate law f w the imn-t,hnlliurn redur system (pp. 12!J-130) mifhovt n thalliurn(I1) inter- mediate hy oonsidering an imn(I1) dis- prolx,rlionat,ion followed hy a slow twc,- rle~.tron exrhange reaction in ewnpeli- lion with a ~.rlatively slow twwelertrrm inilinl reactim st,ep fdlc,werl by a fast <nmoler.tn,n reavtiun produring iron(II1). Anot.her ~ l n ~ s l , xvr<>rding to the author, is Ihr mechanism for the nitration of an,- n~ntin rmripounds. This is not quite tt.ne since I h k e has rerently found that I , enm~e and SO-.' apparently do not reart, i.~,grll~c:~~-uxrept. in the presenre oi probnn swwengetx.

Althc,ugh r,lmnges in other items of r~ntlenl and st.yle have oerurred to the I ~ ~ P W P I . , all and all, t,he hook is quite g w d and is t,o he recommended to all ciudents and tearhers of inorganic <:hem- islyy in particular, and to all other acien- l ids who are int.erested in what is happen- i l~g in this resurging area uf chemical re- search. This monograph may help lead the way luwnrd innking reaction mechmiams as useful in teaching inorganic rhemist,ry as stmclural tdatimships seem t,o Ire a t 1"'"""'t.

R ~ N A L D D. ARCHER Tulane TJniverstly

New Ovleans, Louisiana

A888 / Chemical Education

Quantum Bioehemirtry

Bernard Pullman, Sorhonne, France, and Alberfe Pullman, Centre National de la Rerherche Seientifique. Inter- science Publishers (a division of John Wiley and Sons, Inc.), New York, 1963. xvi + 867 pp. Figs. and tables. 16 X 23.5 cm. $27.50.

This is truly s, monumental book, in- volving great effort to accumulate so many biochemical observations and inter- pret them on the hasis of Hiickel molecular orbital (HMO) calculations.

The book includes (1) a concise, 200- page outline of the HMO method, (2) the sppliestion of HMO calculations to hio- logically important molecules and (3) it

150-page appendix of results of HMO calculations for biologically important molecules. A second volume, to cover both spectra and the role of metal ions, is promised.

A reader onfitmiliar with HMO c a l d a - tions may find the outline too concise, with few examples and no exercises, and encounter difficulty in attempting to do any ealculatiuns himself. For such pur- poses I would recommend Streitwieser's "Mnlecular Orbital Theory for Organic Chemists" or Roberts' "Molecular Orhital Calculations." Also, the present,ation would have been improved by greater emphasis on perturbation methods, whereby, for example, the effect of N- methylation on electron-donor properties of purines would be much clearer than is

apparent from complete calculations, summarized in a. table.

The most remarkable feature of the book is the amitsing success which the suthors claim for HMO calculations on biochem- icals, all the more remarkable in view of their notoriously limited applicability to hydrocarhans. A little skepticism would not have been mieplaeed.

A large majority of the successes are in situations where the result is obvious on chemical grounds: the formylation of gly- cinamide on the amino nitrogen rat,her than an the amide nitrogen, the direction of hydration of crotonyl-CoA, the a- carhonylation of propionyl-CoA, and the fact that dithionite does not reduce D P N t analogs with elect,ron-donating substit,. uents, to mention a few. I t is especially unnecessary t o invoke the "dipositive chnraeter" of hydrolyaahle bonds to show that, among others, amides can he hydro- lyzed, but that in allantoin an imide is mare readily l~ydmlyeed.

Too often, poor correlations are con- c d e d by presenting them as tables, rather than as graphs, as, for example, the rate of oxidation of purines by xanthine oxidase (p. 2G4f). For some eontro- versial points, such as semiconductivity of proteins or relative basicities of purines and pyrimidines, the authors find i t nec- essary to invoke SCF raleulations. Other cases are oversimplified, such as omission of d orbitals of phosphonrs and sulfur, and the entire section on iron porphyrins. (A full-page tahle of MO energy levels,

(Cmfinued o n page A890)

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lmsrd ( l i t Ileberr,;~t,,m pantmeters for Fe and N, is I r s ~ l l y rneimingiul if the calrula- timm :me not related to experimental d:da.)

The mr,st outrngeons example of bhe aufhws' ove~.rrerlulc,us arceptsnre of the success of their ralrulntions is bheir ?on- drrsiw (p. 40%) that experiments of T a y h and Shemmn (.lA(lS, 81, 2Ui.l) verify I.I~ril. interpretnlion of HhlO r:nlrolstions r m tetrs-arninc,plet.idi~~e. The erperi- n len te~ .~ assigned the strurtwe of their prodrwt. on the mxsntplion that the 6- amino group is the most basic. CircuI:u reasoning. rnssquelding as proof, is not Wien??.

Also not wierve is t,lle authors' r r x - ehzsim, "lhnt all l.he essenl.is1 ihinehemival sulrst.nnwa wllir.1~ n w related t,o or per f~rm t,lw h ~ n d i ~ ~ n e n l i ~ l funrtiuns of the living rnatlrr :LIT c<n~stitr~ted of rompletely or, :rl, le;~sl, pi~1.1i:~lly r:irnjrtgated systems" (p. (ii8). The iiuthurs neglect tu rnenticm stntrbl~lal m:tterials and ?ell memh~anes, they glws wer the question of electnm delr,raliaation in proteins and polyphcls- ~ h e l e s , and they st,xte, "The stomids genrt.:tlly lvmsess a ir-elwt~xm fragment m d , i ~ t ~ y ~ w y , seem tc, he in some way in- vr,lvutl in cler%~mn-t,rnnsfer phenomena." (1,. 674).

The wribing is almost nlw~y9 clear, es- rep1 thzl I found tire shwt section o n semin,nduclivity imvildering. (At rrn time is ' ' V ~ L I P I I W Imnd" defined.) The hw,k sufTws ~ I . I ) I I I ~ L N e n o t m m ~ n u m h ~ r of

A890 / Chemical Education

Lypogrr~phiertl ernrra of the stwt h-11ir.h ;I non-scientist (publisher's proofreader) could nrd have been erpecded lo catch, snrh as inro~rect strwtores for u r d (11. 2x41, and a 1,anl~lmer oi cyt,osine (p. 2Oi), a reference to.1. f ! h ~ m . SOC. instearluf J. ?hem. Z'h,!,s. (p . 410), and n st,al.ement (p. 17) t,hat nil sssnmes the values 0, + I , + a , . . . +I, instead of -1,. . . 0, + I , +?, . . . +I. And in the sect,im r,n porphyrins, where the authors ask the reader to nrccpl the results nf group theory, thc symmetries of the- T MO'S are listed (11. 120) as .AI., A?,,, BIVl R3., and El, , rather t,han :I8,,. .I2,,. RhU, &,', and Ev

Mnrh more frequenl. sls en.ot.8 whivl, can m l v hy extreme genewsity he d l r d typographical: I n a frmtnote (p. 51) the aulhors h i m that tho Zpcr* 1\10 is nf lower energy t,han the 2 p r * MO in O?, despite the experiment,al observation thnt O1 is a. gmund-state triplet. The authors claim (1). 34) that, the energy of a dihtumir molecule is a funrticm only of 1;. They rleim (p. 156) thnt tho active species in aromatic sulfonation is tho SO,H+ ion, despite kinetic evidence to the contrary.

Finally, there are many egregious errors of interpretation, hased upon a miwmder- standing of the chemistry and cpiantum mechenir.s involved. The authors claim (p. 130, p. 434, p. 519, p. 551 1 that an MO is antihonding i f and m l y if its energy is a h w e the Coulomb integral for ~ar l ,m. However, for mol~rnles containing heterw at,oms, the zero of energ,v, for purposes of discussing handing, is an average of all Coulomb integrals. Throughout t,he hrmk the sutlrrxs indulge in rskulat,ir,ns in-

volving hyperrnnjogation, surh as for osaloneetir acid, riboflavin, rarotenoids, and even for both a-CH? and P-CHJ of propionyl-CoA (p. 3S1). A spertsrnlar triumph of the authors' calculatims is their rslionalisation (p. 638) of llre direr- tion of wdurlive arylatim of lip+ acid. However, lhis triumph is a s surd merely hy rdlming CHr (and CHI) hyperronjuga- t,inn, hut not CH, wherehy the two sulfur atoms, hnth nttarhed to satnrnt~d rarhons, Iherome nonequivalent,!

The authors pelyetrate perhaps their greatest mirages in the chapter on thia- mine (11. 6 p. G;lOf, p 654). The authom state that C? of thiamine has a net negative chnrgr of 0.134e, "in spite of its loention neat to i~ very elwtlxmegative quaternary nitrogen." What they have apparently forgotten is a footnote (p. 10i -that a for a carhon adjacent to a posi- tive nitrogen will he increased hy 0.:38), snrh that the net negative charge arise. hrranse 01 its Inmtirm (and the use of an nusilinry induotive parameter). They rlnim, by a fantast,ir analogy with aeet- ylene, that this negnt,ive charge renders the h,vdrogen on Cr acidic. In support of their interpretation, they point out that in the nxasolium analog, whirh is inactive, the C2 hears a high posit,ive charge. To explain the slight, sctivity of the N-phenyl analog, despite the increase of negative rhsrge a t Cr, they are forced to invrtke a steria nrpument. Of course, the authors h:rve omitted any consideration of the <I orbitals of sulfur, which mould be ex-

(Conl imed on page ,4898)

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peeted to stabilize what is formally a nitrogen ylide, and they are dearly wrong in their interpretation of the significance of charge densities in HMO calculations.

I n summary, a biochemist who would like to learn MO theory would be well advised to study Streitwieser's hook, a t half the price, and apply those methods to biochemical systems as needed. Some- one who already understands MO theory and its limitations might find this book a convenient introduction to biochemistrv.

CHARLES PERRIB Uniwwity of California

San Diego

Anorganirche Chemie. Volume 3

Istv&n N&ray-Ssab6, Budapest, Hun- gary. Publishing House of the Hun- garian Academy of Sciences, Budapest, 1963. 669 pp. Figs. and tables. 17.5 X 24.5 cm. $14.

This is the third and last volume of this series and continues in the same vein as the previous two volumes. I t covers the element,^ and compounds of Group IB (Copper, Silver, Gold); 11. (Zinc, Cad- mium, Mercury); IIIs (Gallium, In- dium. Thalliumi: Grouo VIII and the

The introduction to each group consists of a comparison of the chemical properties of the elements of the group based on their periodic ehsracteristics. This is followed by a discussion of each element which in- cludes sueh topics as History, Occurrence, Preparation, and Physical and Chemical Properties. A description of the prepam- tion, reactions, and physical and chemicd properties of the compounds follow. The compounds discussed include hydrides, halides, oxyhalides, oxides, compounds formed with the sulfur, nitrogen, and carbon erouns. The czirboxvlates. ni- - . trates, cyanides, eyanates, and isocyanates follow; finally, the coordination com- pounds are discussed.

For each compound the preparation and physical and chemical properties are listed. In mont cases this is done in tabular form summarizing some of the in- formstion available in the literature. These table8 are of value in manv eases as

others. The author indicated in the preface to

the first volume that he had written this series primarily for beginning students in chemistry and for students in related fields such as geology, mineralogy, and engineering. I t was to be of intermediate size, larger than the usual introductory texts hut smaller than the large reference series sueh as Mellor. This goal was seeomplished by Professor N&ray-Szab6. However, such a goal obviously has its shortcomines. Manv unimnortant com-

tant ones the discussion is incomplete. In many cases recent important advances are not included, this is especially true for the Inert Gas compounds in Volume 111.

The paper, printing, and binding of the third volume is superior to that of the first tw,,.

HANS B. JONASSEN Tulane University

New Orleans, Louisiana

Gmelinr Handbuch der Anorgonixhen Chemie. 8. Auflage, System Nummer 58, Kobdt, Teil 8, Liefarung 1

Edited by the Grnelin Instilt& under the direction of E. H. E. Pietsch. Yerlag Chemie, GMBH, Weinheim, Bergstrasse, 1963. rviii + 314 pp. Fig. and t,ables. 17.5 X 25.5 em. $60.50.

This volume serves its a supplement to the portion of Cobalt Part B dealing with "Cobalt I1 Ammines." I t covers the literature on complexes of mono- and divalent cobalt with neutral ligands and "those forming inner complexes." M'ork published through 1949 is evalu- ated exhaustively; pertinent supplement- ary material from 1050-1960 is included. The intention is to supply a survey of the factual material as a supplement to the extensive monograph literature on the theoretical aspects of coordination chemistry.

w. F. K. . ,

1nertGases. pounds are discussed and for many impor- (Continued on page A894)

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