History of Coordination Chemistry in Japan During ... - ACS Publications

Downloaded by UNIV LAVAL on November 2, 2015 | http://pubs.acs.org Publication Date: November 4, 1994 | doi: 10.1021/bk-1994-0565.ch011

Yuji Shibata (1882-1980) in 1942.

Ryutaro Tsuchida (1903-1962) in 1958.

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

Chapter 11

History of Coordination Chemistry in Japan During the Period 1910 to the 1960s Kazuo Yamasaki


Department of Chemistry, Nagoya University, Nagoya 464, Japan

The history of coordination chemistry in Japan is briefly presented. Yuji Shibata, founder of coordination chemistry in Japan studied extensively the absorption spectra of complexes of various metals from 1915 to 1917 after returning from Europe. His researches also included the spectrochemical detection of complex formation in solution, coagulation of arsenic sulfide sols by complex cations, and catalytic oxidation and reduction by metal complexes in solution. Ryutaro Tsuchida published the "spectrochemical series" in 1938 based on the results of his measurements of absorption spectra of cobalt complexes. One of the most remarkable results after World War II is the determination of absolute configurations of cobalt complexes using X-rays in 1954 by Y. Saito and his coworkers.

In this review the history of coordination chemistry in Japan is briefly presented beginning with Yuji Shibata(l882-1980), the only Japanese co-worker of Alfred Werner's. The period covered is from 1910 to the 1960s, about 50 years. Alfred Werner's first paper on the coordination theory (7) was published in 1893 and was introduced to Japan in an abridged form in 1897 by Riko Majima (18741962), who was a postgraduate student in the College of Science, Tokyo Imperial University. Majima, who later became the father of organic chemistry in Japan, introduced this paper and three subsequent papers of Werner's in the Tokyo Kagaku Kaishi (Journal of the Tokyo Chemical Society) under the title of "Theory of Molecular Compounds" (2). If read today, Majima's articles are difficult to under stand even for us who know the coordination theory, indicating that Werner's ideas were not easily understandable at that time.

0097-6156/94/0565-0137$08.00/0 © 1994 American Chemical Society In Coordination Chemistry; Kauffman, G.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.

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Research During the Period 1910-1930s Spectrochemical Works of Shibata and his Co-workers. More than ten years passed before Yuji Shibata carried out the first research on coordination chemistry in 1910. Shibata was born in Tokyo as the second son of Shokei Shibata, an eminent pharmacologist who had studied organic chemistry in Berlin under August Wilhelm von Hofmann during the period 1870-1874. Yuji Shibata graduated from the Department of Chemistry, College of Science, Tokyo Imperial University in 1907. He first studied organic chemistry and published three papers related to the Grignard reagents (3-5). However, he was asked by Joji Sakurai (1858-1939), Chairman of the Department of Chemistry to teach inorganic chemistry because Tamemasa Haga, the professor of inorganic chemistry, was seriously ill, and the university urgently needed a candidate for the future professor of inorganic chemistry. Shibata accepted this proposal and decided to study inorganic chemistry in Europe. Majima, who was Shibata's senior by 10 years and who was staying in Europe at that time, recommended Werner in Zurich, a choice that was to have great consequences. If Shibata had continued his organic chemistry studies or had studied under some other chemists in Europe, coordination chemistry in Japan might have had an entirely different aspect than the present one. When Shibata arrived in Zurich in 1910, it was rumored that Werner might move to a German university, and Shibata decided to study first under Werner's teacher, Arthur Hantzsch (1857-1935) in Leipzig. There Shibata studied the absorption spectra of cobalt (II) salts with a small quartz spectrograph. He found that the color of a solution of a cobalt salt with coordination number six was red, while that of a solution of a cobalt salt with coordination number less than six was blue (6). After staying one year in Leipzig, Shibata moved to Zurich in 1911 to study under Werner. In Zurich he prepared c/5-[Co(NH3)2(en)2]X3 and succeeded in resolving it into optical isomers. This was the first example of the resolution of a [Cob2(AA)2]- type complex, A A and b being didentate and monodentate ligands, respectively (7). In 1912 Shibata moved to Paris to study under Georges Urbain (1872-1938). He intended to study the rare earth elements, but Urbain advised him not to do so because such study required tedious fractional crystallization, which was not suitable for a foreign chemist with only limited time to spend. Instead, Urbain suggested that Shibata carry out absorption spectrographic studies of cobalt complexes. Fortunately, Shibata was able to use the newly obtained medium-sized quartz spectrograph of Adam Hilger, type E2, and he carried out absorption measurements of cobaltammine complexes (8). In Urbains's laboratory Shibata also learned from Jacques Bardet the technique of emission spectrographic analysis, which Shibata later used to analyze the rare earth minerals found in Japan. Shibata returned to Japan in 1913, one year before the outbreak of the First World War, and he was appointed associate professor at his alma mater. Fortunately, he was able to purchase the same medium-sized quartz spectrograph, E2, through the special favor of Joji Sakurai, the Department Chairman, and he actively began spectrochemical studies of metal complexes. This spectrograph was in use for more



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than fifty years in the Department of Chemistry, Tokyo University. The present author also used this quartz spectrograph in 1939 for his doctoral work on the absorption spectra of 2,2'-bipyridine complexes (9-12). During the period 1914-17 Shibata measured the visible and ultraviolet absorption spectra of more than 120 metal complexes, including not only colored complexes of such as cobalt, chromium, nickel, and copper but also those of colorless metals like silver, zinc, and mercury. He published the results in French in the Journal of the College of Science of Tokyo Imperial University during the period 1915-1917 (13-15). These were the world's pioneering works on the absorption spectra of metal complexes, and Shibata was quickly recognized as the foremost specialist in this field. As is well known, absorption spectra were then measured by the so-called Hartley-Baly method, using a Baly tube and photographic plates. It was a semiquantitative method, i.e., the wavelength of the absorption maximum was accurately measured, but the absorption intensity was only qualitative. At almost the same time as Shibata's research Luther and Nikolopulos (16) studied the visible absorption spectra of cobalt-ammines in 1913. Werner himself also began the spectrochemical study of metal complexes (77), but his fatal disease had already begun, and furthermore World War I interrupted the academic activities of European chemists. These were the main reasons why no coordination chemist in Europe carried out detailed spectrochemical studies of metal complexes. In 1921 Shibata devised a spectrochemical method for detecting complex formation in solution (18,19). The so-called method of continuous variation, reported by Paul Job (20) in 1925, involves the same principle as Shibata's method. By using this method Shibata, with his student Toshi Inouye, studied the complex formation between HgCl2 and chlorides of other metals. Works other than Spectrochemical Studies. Shibata extended his study to coagulation studies of negatively charged arsenic sulfide sols by complex cations, and he confirmed the extension of Freundlich's relationship between the coagulation concentration and the cation valency to higher valencies (27). This method was used to determine the ionic charge of a complex cation, together with the conductometric method developed earlier by Miolati and Werner (22,23). A similar experiment for the determination of anionic valency was later carried out in 1953 by R. Tsuchida, Akitsugu Nakahara and Kazuo Nakamoto using positively charged Fe(OH)3 sols (24). In 1917 Shibata and his student Toshio Maruki (25) proposed the c/j-structure of the two ammine groups of Erdmann's salt, NH4[Co(N02)4(NH3)2], based on the fact that its derivative X[Co(C204)(N02)2(NH3)2] was resolvable into optical antipodes. This result was confirmed by William Thomas (26), while E.H.Riesenfeld and R.Klement (27) in 1922 and Bhabes Chandra Ray (28) in 1937, by denying the above-mentioned optical resolution, claimed the salt possesses the rrarcs-structure. This problem of the structure of Erdmann's salt was finally solved in 1957 by Yoshimichi Komiyama, who determined its ira/w-structure by X-ray crystal analysis (29). The reason for such confusion may have been the difficulty in measuring the small rotation angles of a colored complex solution by the visual method. The



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corresponding cw-isomer, K[Co(N02)4(NH3)2], which has been a long standing x missing link in a series of nitroammine complexes, [Co(N02)x(NH3)6-xP" (x=l-5), has recently been isolated and its crystal structure determined by Takashi Fujiwara et al. (30). Shibata's research field was further extended to the study of the catalytic property of cobalt complexes. In 1918 he and his elder brother, Keita Shibata (18771949), professor of phytochemistry and plant physiology at Tokyo Imperial University, found that myricetin, a kind of flavonol, is easily oxidized in solution by cobalt complexes at room temperature, and they published the results in 1920 (31). This study was continued for more than 20 years both in the laboratories of phytochemistry and inorganic chemistry with many co-workers, including Ryutaro Tsuchida and the present author. The primary experimental technique used was the measurement of oxygen absorption by a Warburg manometer; pyrogallol and other oxidizable substances were used as the substrate. The most active compounds were cobalt complexes containing anionic ligands such as [CoCl(NH3)5]X2, whereas complexes such as [Co(NH3)6]X3 were inactive. In addition to cobalt some complexes of copper and nickel were active, but those of chromium were inactive. The catalytic oxidation was studied mainly by oxygen absorption alone because the dark colors of the oxidized solution disturbed the absorption spectral measurements. Thus the details of reaction processes were not easily elucidated. The so-called asymmetric oxidation of optically active substrates such as /-dioxyphenylalanine(Z-dopa) and d-catechin by optically active cobalt complexes such as [CoCl(NH3)(en)2]X2 was also studied with some positive results (32,33). As the oxidation mechanism the Shibata brothers proposed the activation of water molecules which were replaced by the aquation reaction of anionic ligands in a complex ion. They summarized the results of their early 16 papers, and in 1936 they published a book Katalytische Wirkungen der Metallkomplexverbindungen (34). This book was not frequently cited in the chemical literatures of English- speaking countries probably because it was written in German, and the publication was close to the outbreak of World War II. In 1974, however, 40 years after the publication of this book, Eastman Kodak Co. requested a US patent on the use of a cobalt complex such as [Co(NH3)6]Cl3 as an amplifier in the development of color films (35). Although no reference is made to the works of Shibata, it is supposed that the chemists at Eastman Kodak Co. studied the works of Shibata and co-workers. On reaching the retirement age of sixty of the Tokyo Imperial University in 1942 Yuji Shibata moved to the newly established Nagoya University as the Dean of the Science Faculty. Thus the research on catalytic oxidation was suspended, although this research was his favorite topic. His work on the catalytic action of metal complexes was further extended by his co-workers to the catalytic reduction in hydrogen, which had been initiated in 1939 by Shibata himself. Among the results obtained, the formation of [Co(CN)5H]3", a strong reducing agent, reported by Masaakira Iguchi(56) in 1942, was remarkable, and its structure has been extensively discussed (37).



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Works of Other Researchers. Before 1930 studies on coordination chemistry in Japan were almost exclusively concentrated in Yuji Shibata's laboratory, and only a few reports from other laboratories were published. For instance, Satoyasu Iimori (1885-1982), who later became the founder of radiochemistry in Japan, studied the replacement of C N - groups in the hexacyanoferrate(III) ion with water in 1915 (38) and photochemical reactions of cyano complexes of platinum and nickel and photo chemical cells in 1918 (39). Furthermore, measurement of formation constants of nickel, cadmium, and zinc cyano complexes by Koichi Masaki were reported in 1931 (40-43). Another interesting paper (44) on the effects of chemical bonding on the X-ray absorption edges using metal complexes was reported in 1927 by Shin-ichi Aoyama, Kenjiro Kimura, and Yosio Nisina, who were staying in Bohr's research institute in Copenhagen. In 1930 the Department of Chemistry was established in Osaka University, and Ryutaro Tsuchida( 1903-1962) was appointed the professor of inorganic chemistry. Also Taku Uemura(l893-1980) began the research on coordination chemistry at the Tokyo Institute of Technology at nearly the same time. Both men were former co-workers of Yuji Shibata's. Thus young coordination chemists graduated from these newly established laboratories, and the numbers of published research papers gradually increased. Research During the Period 1930-1945 Because the number of researches in this period increased considerably, only the main works will be mentioned. Spectrochemical Studies. In the newly established laboratory Tsuchida began to measure quantitatively the absorption spectra of cobalt complexes, first by remeasuring the absorption spectra reported by Shibata and then preparing new complexes with various ligands. The results were summarized in the shift rules of absorption bands with the replacement of ligands, i.e., the spectrochemical series, which was reported first in 1938 (45) and was refined in 1955 (46). Its importance was recognized after World War II by its relation to the crystal field theory. In this field of research important works of physicists such as Yukito Tanabe and Satoru Sugano after the war deserve mention (47). In 1938 Tsuchida devised a method for measuring the absorption spectra of crystals by combining a microscope and a spectrograph (48). This method was later used by him and his co-workers for measuring the dichroism of crystals (49). In 1939 Tsuchida further proposed a theory that the electron pairs used for coordinate bonds and the unshared electron pairs of the central metal atom are distributed in a symmetrical way around the central metal (50,51). This idea antedated the similar theory proposed in 1940 by Sidgwick and Powell (52), but Tsuchida's works were not known to foreign chemists because of war.


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Preparation of New Compounds. In 1938 Tokuichi Tsumaki prepared a cobalt complex with salicylaldehyde-ethylenediimine and found that it combined reversibly with oxygen (53). This compound provided the impetus for the detailed studies during the war by Melvin Calvin and his co-workers on oxygen adducts of cobalt complexes (54). Tsuchida and Kobayashi prepared a cobalt complex of dimethylglyoxime, a nonelectrolyte, and to prove its structure by its resolvability or nonresolvability, they devised a method called asymmetric adsorption on optically active quartz powder (55). This method was improved in 1970 by Yuzo Yoshikawa and Kazuo Yamasaki using Sephadex ion exchanger for the complete chromatographic resolution of metal complexes (56,57).


Research Activities after World W a r II After the war, which caused tremendous damage all over Japan, the educational systems were reformed, and many new universities were established, which were smaller in size than the earlier universities. With the reconstruction of Japan research in coordination chemistry has become an active field and has been extended to nonWerner type complexes and organometallic chemistry. Only a few postwar researches will be mentioned here. One of the most remarkable results in the field of structural studies is the determination of absolute configurations of the optically active cobalt complex ion [Co(en)3)]3 by Yoshihiko Saito et al. in 1954, using the anomalous scattering of X rays (58,59). This work has expanded enormously, and absolute configurations of about 150 complexes are known as of the end of the 1970s, 80 of which have been determined in Japan (60). Another work to be mentioned is the new synthetic method for cobalt (III) complexes starting from [Co(C03)3]3~ ion, which was devised by Muraji Shibata of Kanazawa University in 1964 (67). This method has been much used to synthesize many new cobalt complexes (62). Finally, it may be appropriate to describe here the national meeting of coordination chemists. The first symposium on coordination chemistry was held in 1942, and eight papers were presented. After World War II it was reorganized, and the first meeting was held in 1952. It continues to the present day. About 700 chemists attended in 1993. In 1970 Japanese coordination chemists organized a small society, the Japan Society of Coordination Chemistry. The above mentioned symposium is held by this Society jointly with the Chemical Society of Japan. In 1961, when the Sixth International Conference on Coordination Chemistry (VIICCC) was held in Detroit, Michigan, U.S.A., several Japanese coordination chemists were invited, which strongly influenced their research. Ryutaro Tsuchida was invited, but his health was not good enough to permit him to go abroad. In 1962 he died of stomach cancer at the age of 59. Five years later, in 1967, the 10th ICCC was held in Japan at Tokyo and Nikko with Yuji Shibata as the President and the present author as the General Secretary of the Organizing Committee, respectively. Many foreign coordination chemists participated in this ICCC, including John C. Bailar, Jr., Fred Basolo, Ronald +


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S. Nyholm, G. Wilke, Κ. B. Yatsimirskii, Lars Gunnar Sillén, Jannik Bjerrum, and other eminent coordination chemists. This conference made a strong impact on the Japanese coordination chemists, especially on the younger ones. Also, foreign chemists had the opportunity to recognize the state of coordination chemistry research in Japan. After working in Tokyo University for 29 years ( 1913-1942), devoting the latter half of his life to the establishment of Nagoya University (1942-1948) and Tokyo Metropolitan University (1949-1957) in the difficult years during and after World War II and serving as the President of the Japan Academy for eight years(1962-1970), Yuji Shibata, the founder of coordination chemistry in Japan calmly passed away on the morning of January 28th, 1980, his 98th birthday. Acknowledgment. The present author is grateful to the Editor , Professor George B. Kauffman for his advice and linguistic revision of the manuscript. Literature Cited Papers marked with * are in Japanese. 1. Werner, A. Z. anorg. Chem. 1893, 3, 267. For a discussion and an annotated English translation see Kauffman, G .Β. Classics in Coordination Chemistry, Part1:The Selected Papers of Alfred Werner; Dover: New York,1968; pp 5-88. 2.* Majima, R. Tokyo Kagaku Kaishi 1898,19,233. 3. Shibata,Y. J. Chem. Soc. 1909, 95, 1449. 4. Shibata,Y. Ber. 1910, 43, 2619. 5. Shibata, Y. J. Chem. Soc. 1910, 97 , 1239. 6. Hantzsch, Α.; Shibata, Y. Z. anorg. Chem. 1912, 73, 309. 7. Werner, Α.; Shibata, Y. Ber. 1912, 45, 3287. 8. Urbain, G.; Shibata, Y. Compt. rend. 1913, 157, 594. 9. Yamasaki, K. Bull. Chem. Soc. Japan 1937,12, 390. 10. Yamasaki, K. Bull. Chem. Soc. Japan 1938, 13, 538. 11. Yamasaki, K. Bull. Chem. Soc. Japan 1939, 14, 130. 12. Yamasaki, K. Bull. Chem. Soc. Japan 1939, 14, 461. 13. Shibata Y. J. Coll. Sci. Imp. Univ. Tokyo 1915, 37, Art.2, 1. 14. Shibata, Y. J. Coll. Sci. Imp. Univ. Tokyo 1916, 37, Art.8, 1. 15. Shibata, Y. J. Coll. Sci. Imp. Univ. Tokyo 1917, 41, Art.6, 1. 16. Luther, R.; Nikolopulos, A. Z. physik. Chem. 1913, 82, 361. 17. In his letter addressed to Shibata with the date of Dec. 28, 1913 Werner wrote, "Thank you very much for your friendly congratulations for the Nobel prize. I am very pleased to learn that you still remain faithfully in metal -ammines. We have also investigations on the absorption spectra going on, which, however, shall never disturb your work. I wish you best results" (translatedfromthe German). Private communication of Shibata to Yamasaki. 18. Shibata, Y.; Inoue, T.; Nakatsuka, Y. Japanese J. Chem. 1922, 1, 1. 19. Shibata, Y.; Inoue, T. Japanese J. Chem. 1926, 2, 109.



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20. Job, P. Compt. rend. 1925, 180, 928. 21.*Matsuno, K. Tokyo Kagaku Kaishi 1918, 39, 908. 22. Werner, Α.; Miolati, A. Z. physik. Chem. 1893, 12, 35. For discussions and English translations see Kauffman, op.cit., pp 89-139. 23. Werner, Α.; Miolati, A. Z. physik. Chem. 1894, 14, 506. 24.*Nakahara, A;Nakamoto, K; Tsuchida, R. Nippon Kagaku Kaishi 1953, 74, 488. 25. Shibata, Y.; Maruki, T. J. Coll. Sci. Imp. Univ. Tokyo 1917, 41, Art.2, 1. 26. Thomas, W. J. Chem. Soc. 1923, 123, 617. 27. Riesenfeld, E.H.; Klement, R. Z. anorg. Chem. 1922, 124, 1. 28. Ray, B.C. Indian Chem. Soc. 1937, 14, 440. 29. Komiyama, Y. Bull. Chem. Soc. Japan 1957, 30, 13 30. Fujiwara, T.;Fuyuhiro, A.;Yamanari, K.; Kaizaki, S. Chem. Lett. 1990, 1679. 31.*Shibata, Y.;Shibata, K. Tokyo Kagaku Kaishi 1920, 41, 35. 32. Shibata, Y.; Tsuchida, R. Bull. Chem. Soc. Japan 1929, 4, 142. 33. Shibata, Y.; Tsuchida, R. Bull. Chem. Soc. Japan 1931, 6, 210. 34. Katalytische Wirkungen der Metallkomplexverbindungen; Shibata, K.;Shibata, Y. Eds.; The Iwata Institute of Biochemistry: Publication No.2; Tokyo, 1936. 35. Eastman Kodak Co., U. S. Patent, 3841873 (Oct. 15, 1974); CA, 1975,37293. 36.*Iguchi, M. Nippon Kagaku Kaishi 1942, 63, 634. 37. King, N.K.; Winfield, M.E. J. Am. Chem. Soc. 1961, 83, 3366. 38.*Iimori, S. Tokyo Kagaku Kaishi 1915, 36, 150. 39.*Iimori, S. Tokyo Kagaku Kaishi 1917, 38, 507. 40. Masaki, K. Bull. Chem. Soc. Japan 1929, 4, 190. 41. Masaki, K. Bull. Chem. Soc. Japan 1931, 6, 60. 42. Masaki, K. Bull. Chem. Soc. Japan 1931, 6, 89. 43. Masaki, K. Bull. Chem. Soc. Japan 1931, 6, 233. 44. Aoyama, S.; Kimura, K.;Nisina, Y. Z. Physik 1927, 44, 810. 45. Tsuchida, R. Bull. Chem. Soc. Japan 1938, 13, 388. 46. Shimura, Y.; Tsuchida, R. Bull. Chem. Soc. Japan 1956, 29, 311. 47. Tanabe, Y.; Sugano, S. J. Phys. Soc. Japan 1954, 9, 753. 48. Tsuchida, R.;Kobayashi, M. Bull. Chem. Soc. Japan 1938, 13, 619. 49. Yamada, S.; Tsuchida, R. Bull. Chem. Soc. Japan 1952, 25, 127. Subsequent papers are published in the same journal through 1960. 50. Tsuchida, R. Bull. Chem. Soc. Japan 1939, 14, 101. 51. Tsuchida, R.;Kobayashi, M.; Kuroya, H. Rev. Phys. Chem. Japan 1939, 13, 151. 52. Sidgwick, N. V.;Powell, C. F. Proc. Roy. Soc. 1940, A176, 153. 53. Tsumaki, T. Bull. Chem. Soc. Japan 1938, 13, 252. 54. Calvin, M.; Bailes, R. H.; Wilmarth, W. K. J. Am. Chem. Soc. 1946, 68, 2254. 55.*Tsuchida, R.; Kobayashi, M.; Nakamura, A. Nippon Kagaku Kaishi 1935, 56, 1339.


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56. 57. 58. 59. 60.

Yoshikawa, Y.;Yamasaki, K. Inorg. Nucl. Chem. Lett. 1968, 4, 697. Yoshikawa,Y.; Yamasaki, K. Coord. Chem. Rev. 1979, 28, 205. Saito, Y.; Nakatsu, K.; Shiro, M.; Kuroya, H. Acta Cryst. 1954, 7, 636. Saito, Y.; Nakatsu, K.; Shiro, M.; Kuroya, H. Acta Cryst. 1955, 8, 729. Saito, Y. Topics in Stereochemistry; Eliel, E. W.; Allinger, N. L. Eds.; John Wiley: New York, 1978, Vol.10; pp 95-174. 61. Shibata, M.; Kyuno, E.; Mori, M. Inorg. Chem. 1964, 3, 1573. 62. Shibata, M. Modern Syntheses of Cobalt (III) Complexes; Topics in Current Chemistry; Springer-Verlag: Berlin, 1983, Vol. 110, pp 1-118. 1994


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