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A Stereochemical Achievement of the First Order: Alfred Werner's Resolution of Cobalt Complexes, 85 Years Later

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A Stereochemical Achievement of the First Order: Alfred Werner's Resolution of Cobalt Complexes, 85 Years Later 50 Bull. Hist. Chem. 20 (1997) A STEREOCHEMICAL ACHIEVEMENT OF THE FIRST ORDER: ALFRED WERNER'S RESOLUTION OF COBALT COMPLEXES, 85 YEARS LATER Gr . Kffn, Clfrn Stt Unvrt, rn Listen, old man; take my advice. Give me the cobalt in a thrice. Though Hell and Devil say me nay, I shall resolve cobalt today (1). With these words the Old One (der Alte, i.e., Werner) challenges the King of the Spirits (Geisterkönig). Spurn- ing the tempting gifts offered him by the King, he ap- proaches the giant blue octahedron with a cry of "I want to resolve cobalt" (Ich will das Kobalt spalten). He tears one side of it away with his axe, removes the d-form, and spins it on his little finger. As everyone joyfully shouts, "It rotates, it rotates!" (Es dreht, es dreht!), der Alte removes the /-form from the other side of the octa- hedron and spins it on his little finger in the direction opposite to the d-form. Now that the momentous task has been accom- plished, all the participants face the audience and tri- umphantly sing the final chorus to the melody of Das Studium der Welber: From early morn still night so late We'll just rotate, rotate, rotate, Until the world and all therein Alfred Werner (1866-1919) from George B. Kauffman, "Alfred Werner-Founder of Coordination Chemistry," Rotating spins to oblivion (2). Berlin-Heidelberg-New York: Springer 1966, Frontispiece So ends the anonymous 1911 Weihnachtskommers (tra- ditional student Christmas party) playlet in verse, Drehen purports to tell in mock-heroic fashion the story of the and Spalten (Rotating and Resolving) (3), whose au- first successful resolution of an optically active coordi- thorship the late Nobel Chemistry laureate Paul Karrer nation compound, a problem that had occupied Alfred (Ph.D., Universität Zürich, 1911) admitted to me. It Werner (4) and a series of his students "over a period of Bull. Hist. Chem. 20 (1997) 51 some nine years" (5), according to his American Werner and King's resolution, all these compounds had Doktorand Victor L. King (1886-1958) (Ph.D., involved atoms of tetrahedral configuration (10). Universität Zurich, 1912) (6), who finally solved the Werner's work, on the other hand, involved a compound problem. King, who was accustomed to being greeted of the octahedral configuration, which he had proposed on the streets of Zürich with the inquiry, "Nun, dreht es in his first paper on the coordination theory (1893) (11) schon?"(Well, does it rotate yet?), recalls how he walked but which was still unproven. As a result of this work, into Werner's office with the long-awaited news. Werner "The spatial configuration of the co-ordination complex "leaned back in his chair, smiled, and said not a single with six associating units is now as firmly established word" (5). as that of the asymmetric tetrahedral carbon atom" (12). All the students knew that something extraordinary The resolution of optically active coordination com- must have happened when the always punctual Werner pounds, a feat that "shook chemistry to its innermost failed to appear at his 5 P.M. lecture. A young student foundations" (13), gained for Werner and his coordina- appeared, announcing that the lecture had been canceled. tion theory the widespread recognition for which he had Werner, fearing that the optical antipodes might racem- been striving so long. In 1913, two years later, largely ize, worked late into the night with King, making many because of this "most brilliant confirmation of [his] ste- derivatives and measuring their rotations. But his fear reochemical views" (14), Werner was awarded the Nobel was unfounded, for the enantiomorphs proved to be re- Prize in Chemistry "in recognition of his work on the markably resistant to racemization in solution, both on linkage of atoms in molecules by which he has thrown prolonged standing and even on heating to incipient new light on earlier investigations and opened up new boiling (7). fields of research especially in inorganic chemistry" (15). Werner atypically but elatedly accosted casual ac- quaintances to tell them of his greatest experimental tri- Wrnr Erlr rh n Optl umph — a "stereochemical achievement of the first or- Atvt der. (8)" Peter Debye offered his own personal account Contrary to common belief, Werner did not mention (9): optical activity in his first paper on the coordination On rl ftrnn hn I nt fr th l t theory (11). It was not until 1899, the same year in which th h Inttt ftr lnh Wrnr hld he accomplished his first resolution — that of the or- fr th ppt d f th ätr It trnd ganic compound, trans-hexahydrophthalic acid — with t tht h ntd t tl t bt th ft tht h his assistant Hermann Erich Conrad (Ph.D., Universita hd dd n n rdntn pnd Zurich, 1898) (16) that he and A. Vilmos considered hh hd rttn f th pln f plrztn I vr h ntrtd ndd bt dd nt t for the first time in print the fact that molecular asym- ndrtnd h h tld t n hd hd n metry for certain types of complexes containing chelate ntf dn t ll bfr tht t ligands (17) is a geometric consequence of his postu- lated octahedral configuration (1 The concepts of asymmetry and optical activity, although introduced fairly late into inorganic chemistry, have h fr th xltdthlndnblt lt played a central role in organic chemistry. If modern [drn b(thlndnxltblt(111 lt organic chemistry is considered to begin in 1828 with (19 nd lr pnd prdt n Friedrich Wöhler's synthesis of urea, then Jean Baptiste tp f r hh bln t th l f - tr r f hh ntl n th l r- Biot's discovery of optical activity in 1812 antedates bn tr nd th llr tr f th the very genesis of this field. Furthermore, Le Bel and ntl [lhxnhxnl] r nn (19 van't Hoff's concept of the tetrahedral carbon atom in 1874, which constitutes the foundation of stereochem- The first evidence that Werner had recognized that reso- istry, was proposed primarily to explain the optical isom- lution of such compounds would provide an elegant, erism investigated by Louis Pasteur and others. It is to definitive proof of his stereochemical views and that he Werner, however, that we owe the systematic introduc- was actually attempting to resolve them is found in a tion of the concept of optical activity into coordination letter of February 20, 1897 to Arturo Miolati antedat- chemistry. ing this paper by two years (20): Although compounds containing asymmetric atoms At prnt r rhn fr trll n- other than carbon, e.g., nitrogen, phosphorus, sulfur, trtd blt ll Wll t b fl ? selenium, tin, and silicon, had been resolved before 5 ll t Ch (1997 Kn tt f th t tht Wrnr hd pnt n ations and had been studying Madame Curie's work nfl rltn th nrvtv n on radium for that purpose. After having made these Mr thn dd ftr th lttr tll 2000 separate fractional crystallizations which proved ldd Wrnr bt h hd nt bndnd h l (1 that the opposite ends of the system were precisely alike and that we had to do something more drastic, I I see from your beautiful paper in the Berichte that proposed increasing the dissimilarity of the you have been more successful in resolving diastomers [sic] by using brom camphor sulfonic acid propylenediamine than we have. Now I wish to ask as a salt-forming constituent having extremely high you whether you would permit me to use the active optical activity. When this was tried, the isomers in propylenediamine in the investigation of compounds the form of these salts literally fell apart. [(O 2N) 2Copn2 ]X, of which we have already obtained five inactive series. A ltn f th hlr- r br- r lt was trtd th ltn f th rlvn nt hr- Further proof f ntnn tvt n th fld pn th (+(+-dtrr prpttd nd r- pl n th Wrnr lltn f plx lbld vd b fltrtn ( h (--dthnt prp- "ltn xprnt n [CCO 3n2]r [n = thl- ttd fr th thr lr b ddtn f d ndn] b n f lvr d-trtrt /I 19 dthnt h rrtllzd (+(+-dtrr b" ( It n th pnd tht Kn b- trtd th nntrtd hdrhlr d t ld n xprntl r n frt rrvn n rh (23), prptt f th (+-hlrd hl th (--hlrd but after r f nfl ttpt t rltn prpttd b rndn th (--dthnt th nn- h bndnd t trtd hdrhlr d flld b ln h pr- dr rprdbl (7 nd h bn dfd nd Wrnr nd Kn ltn plfd fr l xprnt fr th ndr- Wrnr h th t dl d thd f rl- rdt nrn lbrtr ( tn tr dtrr frtn hh ftn h rltn hh Wrnr ndrd t n- fld b th ntrll rrn ptll tv fr "n f th t fr-rhn nln f th d nd b thn vlbl fr rlvn nt thdrl frl" prvd tht "tl t n act r nd thr lt r nt vr tbl n l- ntrl t f tbl trll ntrtd tn Kppn nd p nth fr ntrll - ll [nd] tht pr llr pnd [r- rrn (+-phr f rlvn nt tht r trn dntn pnd] n l r tbl rrr d r b h (+-phrlfn nd (+- r hrb th dffrn btn vln brphrlfn d prvdd Wrnr nd Kn pnd [rdnr pnd] hh tll fr- th th nt tht fnll brht th ( ntl ntnd dppr ntrl" ( Ard- h rltn nvlvd t r f plx — n t Kn t "th lt prf fr th thdrl th -nhlrb(thlndnblt(III frl d b A Wrnr" (9 lt [CCl(3n] (th Kn nd th rr- Wrnr nr ntrbtn t rdntn pndn -br- lt [Cr(3n] (th htr t tnd t br th ft tht h Wrnr Privat-Assistent Ernt Shlz h trnd ndr Arthr ntzh n rn h- Unvrtät ürh 1911 (5 h lttr r r t th n ph n trhtr was rnll t rlv b f th rtr dffrn n lblt lld t Unvrtät ürh t th rn htr btn th dtrr tht r frd th th r- nd nt nd th n ltr n nrn h- lvn nt lvr (+-3-br-9-phrlfnt tr ntl th ntr tr 19/3 (f pp 3- r bth r th (+-brphrlfnt f th 39 It nt ntl 19 hn h rpttn frl (+-ntpd l lbl thn tht f th (--ntpd tblhd n rdntn htr tht th nbr Ardn t Kn lbrtr ntb (f 3 f h nrn rtl — 1 — rhd tht f h r- p 1 ndtd bt t btn Aprl nd n n ppr (3 1 1911 "Wth th rn Reihe [r] th hrfr th tn t h t t Wrnr dxtr lt fll rht t nd n frtntn n- ln t d n rlvn rdntn pnd r" Kn ltr rlld (5 nt nl n ntrtn bt ltt n (31 Mn nn plx h xlt pnd hh I shall never forget the day that the optically active ntn th hlt lnd th hh Wrnr frt n- isomers were first attained.
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