Coordination Chemistry - American Chemical Society

Chapter 23

Inorganic Optical Activity R. D . Gillard

Downloaded by PENNSYLVANIA STATE UNIV on July 23, 2013 | http://pubs.acs.org Publication Date: November 4, 1994 | doi: 10.1021/bk-1994-0565.ch023

Department of Chemistry, University of Wales, Cardiff, CF1 3TB Wales, United Kingdom

This account plaits three major inorganic threads: stereochemistry and optical activity; qualitative analysis; and aqueous coordination chemistry. Knowledge of the phenomena of optical activity has grown largely through inorganic systems, from Biot (quartz), through mineralogy (Haidinger— circular dichroism) and crystal properties (e.g., the spontaneous resolution of sodium chlorate), to the Cotton effect and the resolutions of Werner's cationic hexol and Mann's anion. The stereochemistries of oligosulfides of the platinum metals are described. [PtS ] (e.g.,x = 15) can be resolved through diastereo- isomeric salts with (+)-[Ru(bipy)3] . When preparations of oligosulfides of platinum are controlled carefully, the sole product is optically active (NH4)2[PtS17]·2H2O. This is a unique spontaneous appearance of optical activity in an inorganic molecule. 2-

x

2+

This paper traces the development of optical activity in inorganic compounds to the point where Alfred Werner was able to use optical resolution to such striking effect in proving the octahedral stereochemistry of several metal ions by resolving chelated compounds, in particular the fully inorganic cation now called "Werner's hexol". This achievement came to fruition ( 1) in the years just prior to World War I. The present account brings together the themes which led to that first resolution of a purely inorganic compound, defined as containing no carbon of any kind. These themes are: first, optical activity and its relation to stereochemistry; second, an aspect of qualitative analysis related to the complexation of metal ions, and, finally, chelation in aqueous coordination chemistry. The paper concludes by tracing the development of inorganic optically active compounds since Werner's time. Optical Activity The notion of handedness in physical science arose from John Frederick William Herschel's descriptions (2) of quartz. (Parenthetically, it is worth noting here his discovery of the complexation of silver ions by thiosulfate and his comment that the resulting solutions tasted sweet. The eutropic [Au(S203)2] ~ is also bioactive in "myochrysin", the chrysotherapeutic agent for rheumatoid arthritis.) The now well developed relationship between shape and chiroptical spectroscopy has roots in the 3

0097-6156/94/0565-0286$08.00/0 © 1994 American Chemical Society In Coordination Chemistry; Kauffman, G.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.


23.

GILLARD

Inorganic Optical Activity

287

almost contemporaneous findings of handedness in minerals and Jean-Baptiste Biot's discovery (3) of the rotation of linearly polarized light by liquids. During the hundred-odd years between Biot's first measurements of optical rotation and Werner's resolutions of chiral coordination compounds, this relationship between chiral shapes and optical properties waxed and waned. Chemical systems containing colored transition metal ions lent themselves rather readily to studies of this kind made by eye because magnetic-dipole transitions are common: the optical densities are low and dissymmetries often high. Many of the major developments in optical activity have come from inorganic systems. For example, the great mineralogist Wilhelm Karl Haidinger observed (4) circular dichroism in amethystine quartz. This was contemporaneous (in the 1840s) with the intensive studies of the complexation of copper(II) ions by natural acids. Charles-Louis Barreswils and Hermann Fehling focused on (+)-tartaric acid: JeanBaptiste Joseph Dieudonné Boussingault, the father of food chemistry, on "Leimzucker" (glycine). These cupric aminoacidates have had a leading role in the development of chemistry (chelation—the "Inner Komplexe" of Heinrich Ley and Giuseppe Bruni; the determination of relative optical configuration by Paul Pfeiffer; the "biuret" reaction; isolation of protein hydrolysates; copper bands for rheumatism). It is remarkable that Boussingault's simple compound (5) of 1841, [Cu(N03)(H20)(glycinate)], was not made again (6) for 150 years. In one sense, it was likewise odd that the chiroptical properties of Fehling's solution were not studied for 50 years, until the time of Aimé Cotton, Professor of Physics at the Sorbonne. By then, in the 1890s, measurements of chiroptical proper ties as a function of wavelength had become rare, the interest of a few physicists. (It is worth remembering that, though the phenomena of the Cotton effect (7) of polarized light in the region of an absorption band were known, Le., the anomalous rotatory dispersion, the unequal absorption of left- and of right-circularly polarized light, and the ellipticity of the emergent initially linearly polarized light, it was not until 1915 that Bruhat defined circular dichroism using a differential extinction coefficient, Δε, £L£R). This change may have been due to the invention of the Bunsen burner, which gave a ready source of relatively monochromatic light, in the 1860s. Coupled with the colorless nature of the many natural products beginning to be studied in the developing field of organic chemistry, this gave the extraordinary dominance of [OC]D as the measured chiroptical property. The relationship between the physics and the chemistry of shape, so strong in the French tradition, became weak. In a related way, although Kelvin coined the word "chirality" in the 1880s, it was not widely taken up by stereochemists generally for the best part of a century. In the context of inorganic optical activity, this dominance of [OC]D was ignored by a few, including Werner himself, and, a little later, F . M . Jaeger (8) and (independently) I. Lifschitz, both of Groningen, who routinely measured Cotton effects by optical rotatory dispersion (ORD). The present-day relationship between molecular shape and effects of polarized light was more fully anticipated in the work, on the one hand, of Stotherd Mitchell (9) in Glasgow on production of optical activity by photo-reactions of racemic solutions (including Fehling's) using circularly polarized light and, on the other, by direct measurement in the 1930s of the circular dichroism of Werner complexes by Mathieu (10). Karl Freudenberg's great work (11) of 1933 was perhaps the last to bring together all aspects of stereochemistry. One other aspect of inorganic morphology concerns the handedness of crystals. Indeed, Werner employed this in work on the chirality of crystals of K3[Rh(C204)3]-

In Coordination Chemistry; Kauffman, G.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.

288

COORDINATION CHEMISTRY


4^Η2θ and of [M(C2C>4)(en)2]Br (M = Cr or Co). The organic chemist F.R. Japp (of the Japp-Klingemann reaction) first systematically drew together, in his Presidential Address (12) to the Chemistry Section of the British Association for the Advancement of Science, the possible "Origins of Asymmetry". Work on the statistics of the crystallization of enantiomorphous substances was quite common. Eakle had noted ( 13) in 1896 that aqueous sodium periodate crystallized from sodium nitrate solutions with left-handed crystals in large excess, and there were similar findings by Grégoire Wyrouboff (14) on silicotungstates. A popular subject for such experiments was sodium chlorate, NaC103. In early experiments, of 938 sealed tubes, 433 gave only right-handed crystals, 411 only left-handed, and 94 gave both. The general experience (15) is that, where only a few larger crystals form, there is usually a dominance of one hand, but where many smaller crystals form, the distribution is more even. Qualitative Analysis As part of his magisterial survey of mineral compositions Berzelius devised many analytical procedures which have stood the test of time. Yellow ammonium sulfide was used to part the various metal sulfides precipitated from acid aqueous solutions by sulfane. Some dissolved. This property was known to many if not all nineteenthcentury chemists. The German K . A . Hofmann discovered several fascinating coordination compounds, including platinum blue, "Hofmann's compound", K3[Fe(CN)5(OH2)], and the famous clathrate compound of benzene, Ni(CN)2NH3-C6H6. He undertook a systematic study (16) of the complex compounds which could be isolated from solutions of metal sulfides in yellow ammonium sulfide. These included simple salts of anions like [Q1S4] -, [AUS3]", [PdSn] -, [PtSio] ", [PtSi ] ", and [IrSis] ". The rhodium eutrope of the last has been made only recently (17); the structure of its ammonium salt is known (18). Despite this and the great current interest in these oligosulfides, Hofmann's iridium compound has not been studied since his day. Werner's formulations of these thioanions are interesting; he mentioned (19) the salt, made (20) in 1879 by Sophus Mads Jorgensen, [CrCl(NH3)s](S5), in which the doubly charged pentasulfide ion is simply a counter-ion. However, Werner accepted Drechsel's then plausible suggestion (21) that the pentasulfide ion (actually linear) is structurally related to sulfate and thiosulfate: 3

2

2

2

3

5

K

"S

s

"s

;

s

2

s

K

S

2

s

;

K

s

2

Ο

0

0

o"

"0

0

0

Werner's formulations of Hofmann's compounds were consequently written (19) as: S NH 5

S Pt

4

+ 2H 0

5

2

S5NH4

At almost the same time the correct formulation of Werner's hexol as a trischelate led him to its optical resolution. The earliest suggestion that Hofmann's pentakaideka-


23.

GILLARD

289


sulfidoplatinate ion should be formulated as the ammonium salt of the trischelated (NH4)2[Pt(S5)3]-2H 0 2

seems to be that (22) of Nevil Vincent Sidgwick.


Chelation Werner's initial and monumental article (23), whose centenary we celebrate here, "Beitrag zur Konstitution anorganischen Verbindungen", elucidated the nature of the metal-ammines, with ammonia as an uncharged ligand. Within a short time the stereochemical utility of linking the N-donors into the didentate 1,2-diaminoethane metal-ammines, (en), again uncharged, was utilized. Very rapidly the concept of chelation of charged ligands emerged from the work of Bruni (24) and of Ley (25) on the seemingly anomalous properties of bisglycinatocopper(II). Werner himself later spoke (26) of his own work on acetylacetonates of platinum as having anticipated this concept of "Innerkomplexe", in which the charged (main valency) and uncharged (subsidiary valency) ligands are part of one and the same molecule. Certainly the stereochemical consequences of chelation at a metal ion, whatever the nature of the ligand, whether uncharged en, singly-charged a-aminoacidate, or doubly-charged oxalate, were widely appreciated by 1911. This appreciation led to a rapid increase in the range of resolved chelated ions, like [Fe(bipyridyl)3] or [Co(C204)3] ". However, the "hexol" remained the only resolved inorganic molecule until Frederick G. Mann (27) in 1933 achieved the resolution of the anion cis-[Rh(HNS02NH)2(OH2)2]~ using the cation of an optically active amine (a-phenylethylamine) as the resolving agent. 2+

3

Optically Active Platinum Polysulfides Sidgwick's suggestion (22) that Hofmann's sulfur-rich salt contained the [Pt(S5)3] " ion was borne out by a crystallographic study, using X-ray diffraction (28). The simplest compositions are [Pt(S5)2] " and [Pt(S5)3] . Several salts of both ions are known, prepared in aqueous solution as in equations 1 and 2, following the route (16) of Hofmann and Hôchtlen: 2

2

2_

2

2

[PtCl ] " + 2(NH4)2S -> [Pt(S ) ] - + 4NH C1

(1)

[PtCl ] - + 3(NH4) S -> [Pt(S ) ] " + 6NH4CI

(2)

4

5

5

2

2

4

2

6

2

5

5

3

There are several complications endemic in this system. First, as was common experience from qualitative analysis with arsenic or tin, reagents of either oxidation state, with an excess of yellow ammonium sulfide, give the same higher oxidation state: 2

2

[Pt(S )2l - + 2 S " 5

5

2

2

2

-> [Pt(S ) ] - + S - + S " 5

3

2

(3)

3

Indeed, this tris pentasulfidoplatinate(IV) product of equation (3) is remarkably easy to obtain, being the chief product (29) of reactions designed to yield [PtS ] ~, where χ > 15. Likewise, the ostensibly very stable compound [PtChibipy)] reacts under mild conditions with aqueous yellow ammonium sulfide as in equation (4) to give (30) the oxidized homoleptic [Pt(S5)3] : 2

x

2-


290


2

2

2

2

[PtCl (bipy)] + 4 S " -> [Pt(S ) ] -+ bipy + 2C1" + S ' + S " 2

5

5

3

2

(4)

3

2_

Further, quite apart from this redox activity, the oligosulfides ( S and HS ") of yellow ammonium sulfide are very labile with changing pH. The chain length varies as pH changes, presumably because the values of p K for the dissociations of equation 5 vary markedly depending on the value of x: x

X

a

2

H S H ;=== H+ + HS " =s=? H+ + S " X

X

(5)

x


2

Yellow ammonium sulfide at pH 9 contains more S6 ~ than it does at pH 10. Partly in consequence, the complex anions with platinum also vary. Whereas (NH4)2[PtSi5]-2H20 is the product from preparations at pH 10.5, the product from ostensibly similar solutions at pH 9.5 is (NH4)2[PtSi7]-2H20. An aged solution of this ammonium heptakaidekasulfîdoplatinate(IV) dihydrate undergoes disproportionation as in equation (6): 3[PtSi ] 7

2

->

2[PtS ] " 18

+

2

[PtSisl -

(6)

2

The new complex anion [PtSis] " gave (31) a crystalline salt with the tetraphenylphosphonium ion. The anions were [Pt(S6)3] , with three seven-membered chelate rings; the angles within the rings, S-Pt-S, were much larger than 90°. These systems containing platinum ions complexed by polysulfides are thus chemically rather more complicated than expected. There are also physical complications arising from the details of crystal packing. The salt (NH4)2[Pt(S5)3]-2H20 is dimorphic (32), there being a red-orange form and a quite distinct brown-maroon form. The unit-cell of the second form (33) is about twice as large as that of the red-orange crystals. In both, the complex anion has three fold symmetry, each chelate ring PtSs having a chair-conformation. The same structural features are found (18) in the crystal of the new compound containing rhodium(III), (NH4)3[Rh(S5)3].3H20. As in so many other salts the replacement of ammonium by potassium gives equivalent dimorphism in K2[Pt(S5)3]-2H20. The dimorphic potassium salts are isomorphous with the ammonium pair. In the several solid compounds studied by X-ray diffraction only one conforma tion of the trischelated anion [M(S5)3] (M = Pt, η = 2; M = Rh, η = 3) has been seen; this has three chair-form rings MS5, related by a three-fold axis through the metal ion. In solution, however, these six-membered rings are flexible so other conformations exist where the three-fold axis is lost. Indeed, the P t chemical shift observed for solutions of (NH4)2[Pt(S5)3]-2H20 at room temperatures broadens (34) on cooling and then splits into two sharp signals (with intensity ratio 30:1), indicating the existence of a second conformer. 2

2-

n_

195

Optical Resolutions. In the same manner as for other kinetically inert complex ions with the d electronic configuration, [Pt(S5)3] can be resolved into its enantiomers. Pasteur's method of forming diastereomeric salts with a chiral counterion was applied. The resolving agent, (+)-tris-2,2'-bipyridylruthenium(II), was chosen for two reasons. It has a double charge {to balance that of [PtSis] }, and it can be made by a dissymmetric synthesis. Indeed, an aqueous solution of (NH4)2[Pt(S5)3]-2H20 on treatment with this resolving agent gave (35) one insoluble 6

2_

2-


23.


GILLARD

291

diastereomer. This separation seems ideal; one diastereomeric salt is precipitated fully and the other not at all, giving optically pure [Pt(S5)3] in one operation. The ostensibly similar 1,10-phenanthroline complex cation, (+) [Rh(phen)3] , also gave separation, albeit less clean, when used as a resolving agent for [PtSis] ". The optically resolved [ P t S i s ] ion shows no racemization in the dark. This new inorganic optically active compound has several novel features. Werner's prototype, his "hexol", contained cobalt, a first-row element, and was a cation. F.G. Mann's rhodate, while an anion, contained a second row element. (+) [Pt(S5)3] ~ contains a third-row element. Further, this thioplatinate(IV) shares with the helicene hydrocarbon series the distinction of manifesting molecular optical activity while containing atoms of only two elements. Of course, enantiomorphism is well known in crystalline binary assemblies (as in cinnabar, HgS, or quartz, S1O2) and even in elements (like tellurium). 2_

2+

2

2-


2

Unique Spontaneous Inorganic Optical Activity. The known values of χ in isolated salts of [PtS ] - are 15,17, and 18. The first and last are homoleptic [Pt(S5)3] ~ and [Pt(S6)3] ", respectively. The X-ray photoelectron spectra of the heptakaidekasulfidoplatinate(rV), which can be made optically active, suggests (36) that it is to be formulated [Pt(S6)2(S5)] " rather than [Pt(S5)2(S7)] ". Resolution has been achieved for χ = 15, but not yet for χ = 18. For χ = 17, a remarkable finding is that the product (NH4)2[PtSn]-2H20 is optically active. Yellow ammonium sulfide is made by dissolving elemental sulfur in strong aqueous ammonia using hydrogen sulfide. Sodium hexachloroplatinate(IV) is dissolved in this solution, and hydrochloric acid added until the pH is 9.2. The product of crystallization is optically active (NH ) [PtSi7]-2H 0. 2

x

2

2

2

4

2

2

2

This spontaneous occurrence of molecular optical activity in a purely inorganic compound is unique. Presumably, either enantiomer might be obtained in any single experiment. In the author's laboratory, the first few experiments indeed yielded crystals of one or the other enantiomer, apparently at random. However a single enantiomer, (+), has subsequently been dominant. The phenomenon is presumably related to the handed seeding found for sodium chlorate (15) and, by Werner 80 years ago, for cationic complexes of 1,2-diaminoethane (en) (37). Elucidating this new inorganic optical activity more fully will no doubt extend our appreciation of Werner's extraordinary stereochemical insights.

Literature Cited 1. 2. 3. 4. 5. 6. 7.

Werner, A. Neuere Anschauungen auf dem Gebiete der anorganischen Chemie, 3rd edition; F. Vieweg und Sohn: Braunschweig, 1913. Herschel, J. F. W. Trans. Cambridge Phil. Soc. 1822, 1, 43. Biot, J-B. Nouv. Bull. Soc. Philom. 1815, 4, 26. Haidinger, W. K. Ann. Phys. 1847, 70, 531. Boussingault, J. B. J. D. Ann. Chim. Phys. 1841, 257. Davies, H. O.; Gillard, R. D.; Hursthouse, M. B.; Mazin, Μ. Α.; Williams, P. Α., J. Chem. Soc., Chem. Comm. 1992, 226. Cotton, A. Ann. Chim. Phys. 1896, 8, 347.


292 8.


9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23.

24. 25

26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37.


Jaeger, F. M. Optical Activity and High Temperature Measurements; the George Fisher Baker Lectures at Cornell University; McGraw-Hill: New York, NY, 1930. Mitchell, S. The Cotton Effect; G. Bell and Sons: London, 1933. Mathieu, J-P. Bull. Soc. Chim. France, 1936, 3, 476. Freudenberg, K. Stereochemie; Franz Deuticke: Leipzig und Wien, 1933. Japp, F. R. Report of the 68th Meeting, Brit. Ass. Adv. Sci., Bristol 1898; John Murray: London, 1899; p 813. Eakle, A. S. Z. Krystallogr. Mineral. 1896, 26, 562. Wyrouboff, G. Zentralblatt. 1898, 98, II, 90. Gillard, R. D.; Jesus, J. P. J. Chem. Soc. Dalton 1979, 1779. Hofmann, Κ. Α.; Höchtlen, F. Chem. Ber. 1903, 36, 3090. Krause, R. A. Inorg. Nucl. Chem. Lett. 1971, 7, 973. Cartwright, P.; Gillard, R. D.; Sillanpaa, E. R. J.; Valkonen, J. Polyhedron 1987, 6, 1775. Werner, A. ref. 1; p 151. Jørgensen, S. M. J. prakt. Chem. 1879, 20, 136. Drechsel, Ε. Z. anorg. Chem. 1900, 25, 407. Sidgwick, Ν. V. The Chemical Elements and Their Compounds; Oxford University Press: London, 1950; Vol. 2; p 1622. Werner, A. Z. anorg. Chem. 1893, 3, 267; for a discussion and annotated English translation see Kauffman, G. B. Classics in Coordination Chemistry, Part 1: The Selected Papers of Alfred Werner; Dover: New York, NY, 1968; pp 5-88. Bruni, G.; Fornara, C. Atti R. Acad. dei Lincei Roma 1904, 13, II, 26. Ley, Η. Z. Elektrochem. 1904, 10, 954; for a discussion and annotated English translation see Kauffman, G. B. Classics in Coordination Chemistry, Part 3: Twentieth-Century Papers (1904-1935); Dover: New York, NY, 1978; pp 5-19. Werner, A. ref. 1; p 237. Mann, F.G. J. Chem. Soc. 1933, 412. Jones, P. E.; Katz, L. Acta Crystallogr. 1969, B25, 745. Cartwright, P.; Gillard, R. D.; Sillanpaa, E. R. J.; Valkonen, J. Polyhedron 1991, 10, 2501. Collins, J.; Gillard, R. D.; Hursthouse, M. B. Polyhedron 1993, 12, 255. Sillanpaa, R.; Cartwright, P. S.; Gillard, R. D.; Valkonen, J. Polyhedron 1988, 7, 1801. Krause, R. Α.; Wickenden-Kozlowski, Α.; Cronin, J. L. Inorg. Synth. 1982, 21, 12. Evans, Ε. Η. M.; Richards, J. P. G.; Gillard, R. D.; Wimmer, F. L. Nouveau J. Chimie 1986, 19, 783. Gillard, R. D.; Riddell, F. G.; Wimmer, F. L. J. Chem. Soc., Chem. Comm. 1982, 332. Gillard, R. D.; Wimmer, F. L. J. Chem. Soc., Chem. Comm. 1978, 936. Buckley, A. N.; Wouterlood, H. J.; Cartwright, P. S.; Gillard, R. D. Inorg. Chim. Acta. 1988, 143, 77. Werner, A. Ber. 1911, 44, 1887; 1914, 47, 3087; for discussions and annotated English translations see Kauffman ref.23; pp 155-173 and 175-184, respectively.

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1993


Coordination Chemistry - American Chemical Society

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