1) ( a ) M. Bobtelsky, J. Jordan, J. Am. Chem. Soc., 69, 2286(1947). ( b ) R. W. Green, G. M. Parkins, J. Phys. Chem., 65, 1658(1961). ( c ) J. Stark,
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1 1) ( a ) M. Bobtelsky, J. Jordan, J. Am. Chem. Soc., 69, 2286(1947). ( b ) R. W. Green, G. M. Parkins, J. Phys. Chem., 65, 1658(1961). ( c ) J. Stark, Anal. Chim. Acta, 28, 132(1963). ( d ) C. F. Timberlake, J. Chem. Soc., 1964, ( e ) S. Ramamoorthy, P. G. Manning, J. Inorg. Nucl. Chem., 35, 1571(1973). ( f ) V. Salvada, X. Ribas, Inorg. Chim. Acta, 137, 155(1987). 2) T. J. Hamilton, B. E. Dale, M. R. Ladisch, G. T. Taso, Biotechnol. Bioeng., 26, 781(1984) ; K. W. Lin, M. R. Ladisch, M. Voloch, J. A. Patterson, C. H. Noller, ibid., 27, 1427(1985). 3) J. E. Hanby, Jr., D. C. Johnson, J. Polym. Sci., A-1, 7, 2983(1969). 4) H. Yokoi, Y. Mori, T. Mitani, S. Kawata, Bull. Chem. Soc. Jpn., 65, 1898(1992). 5) H. Yokoi, T. Mitani, Y. Mori, Bull. Chem. Soc. Jpn., to be published. 6) ( a ) B. F. Myasoedov, Z. K. Karalova, V. V. Nekrasoya, L. M. Rodionova, J. Inorg. Nucl. Chem., 42, 1495(1980).
2 7) J. Start, "The Solvent Extraction of Metal Chelates", edited by H. Irving, Pergamon, Oxford(1964) p. 4 F. J. C. Rossotti, H. Rossotti, "The Determination of Stability Constants", McGraw-Hill, New York(1961) p ) G. V. Bakore, S. D. Bhardwaj, Proc. Natl. Inst. Sci., India, A, 29, 90(1963). 10) M. L. Good, S. E. Bryan, F. F. Holland, Jr., G. J. Maus, J. Inorg. Nucl. Chem., 25, 1167(1963) ; M. L. Good, S. C. Srivastava, F. F. Holland, Jr., Anal. Chim. Acta, 31, 534(1964) ; M. L. Good, S. C. Srivastava, J. Inorg. Nucl. Chem., 27, 2429(1965). 11) T. Sato, H. Watanabe, S. Kikuchi, J. Appl. Chem. Biotechnol., 25, 63(1975).
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4 14) D. F. Harvey, C. A. Christmas, J. K. McCusker, P. M. Hagen, R. K. Chadha, D. N. Hendrickson, Angew. Chem. Int. Ed. Engl., 30, 598(1991). 15) E. KOnig, "Magnetic Properties of Coordination and Organo-metallic Transition Metal Compounds, " Landolt-BOrnstein Tables, New Series Group II, Vol. II, Springer-Verlag, Berlin(1966). 16) E. A. Pinheiro, P. P. de Abreu Filho, F. Galembeck, E. C. da Silva, H. Vargas, Langmuir, 3, 445(1987) ; G. Vierke, J. Chenz. Soc., Faraday Trans. 1, 69, 1523(1973) ; L. Yarmus, A. A. Harkavy, Phys. Rev., 173, 427(1968). 17) R. Aasa, B. G. Malmström, P. Saltman, T. VaringArd, Biochinz. Biophys. Acta, 88, 430(1964) ; P. Aisen, R. Aasa, B. G. MalmstrOm, T. Varingard, J. Biol. Chem., 242, 2484(1967) ; T. Caster, Jr., G. S. Newell, W. C. Holton, C. P. Slichter, J. Chem. Phys., 32, 668 (1960) ; H. H. Wickman, M. P. Klein, D. A. Shirley, ibid., 42, 2113(1965) ; R. D. Dowsing, J. F. Gibson, ibid., 50, 294(1969).
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6 18) L. G. Van Uitert, W, C. Fernelius, J. Am. Chem. Soc., 78, 375(1954) ; S. Kirschner, R. Kiesling, ibid., 82, 4174(1960) ; T. D. Smith, J. Chem. Soc., 1965, 2145 ; E. Bottari, M. Vicedomini, J. Inorg. Nucl. Chem., 34, 921(1972). 19) T. G. Spiro, S. E. Allerton, J. Renner, A. Terzis, R. Bils, P. Saltman, J. Am. Chem. Soc., 88, 2721 (1966). 20) T. G. Spiro, L. Pape, P. Saltman, ibid., 89, 5555 (1967).
7 22) P. J. Murphy, A. M. Posner, J. P. Quirk, J. Colloid Interface Sci., 56, 312(1976). 23) C. M. Flynn, Jr., Chem. Rev., 84, 31(1984). 24) T. G. Spiro, G. Bates, P. Sal tman, J. Am. Chem. Soc., 89, 5559(1967). Characterization of the Complexes of Iron(III) with L-Tartrate in the Solvent Extraction System -Formation of Iron(III)-Cluster Complexes- Tsuyoshi MITANI and Hiroshi YoKofil Graduate School of Electronic Science and Technology, Shizuoka University ; Hamamatsu-shi 432 Japan t Department of Applied Chemistry, Faculty of Engineering, Shizuoka University ; Hamamatsu-shi 432 Japan The complexes of iron(iii) with L-tartaric acid (hereafter abbreviated as iron(m)-tartrate complexes) formed in aqueous solutions at various ph values are extracted with (methyl)- trioctylammonium chloride (TOMAC ; R3R'NC1) in toluene. The complex species before and after extraction have been characterized by various techniques. A magnetic susceptibility titration experiment has shown that iron(11i)-tartrate complexes in aqueous solution vary in structure accoriding to the conditions of ph and R=[L-tartaric acid]/[iron(111) ion] and are extracted with TOMAC into toluene from aqueous solution without great changes in structure. The complex species at R=1 (ph 6-12), R=3 (ph 3-12) and R=10 (ph 3-8) are of a type of iron(iii) cluster complexes. It has been revealed that in aqueous solutions at R=3-10 the ratio of tartrate anion to iron(111) ion in the complexes are less than 2 and that this ratio decreases with an increase in ph. The estimated compositions of extracted complexes at R=3 (tart=tartrate anion) are as follows : [(RIR' N),Fe(tart),(OH),.9] (ph 6. 1) [(R3R' N),.2Fe(tart)o.6(OH)3.0] (ph 10. 1) [(R3R' N)0.9Fe(tart)0.3(OH)3.0 (ph 12. 0) It is reasonably considered that the complex species at R=3 (ph10) bear a structural resemblance to ironan hydroxide clusters whose surfaces are modified with tartrate anions. Those negatively-charged carboxyl groups projecting to the outside can make ion-pairs with TOMAC cations and the complex species are extracted in toluene in such a form as reversed micelle. These complexes may be less than several tens A in diameter.
1) Y. Kobuke, K. Hanji, K. Horiguchi, M. Asada, Y. Nakayama, J. Furukawa, J. Am. Chem. Soc., 98, 7414(1976). 2) S. Yoshida, S. Hayano, J. Memb. Sci.,
1) Y. Kobuke, K. Hanji, K. Horiguchi, M. Asada, Y. Nakayama, J. Furukawa, J. Am. Chem. Soc., 98, 7414(1976). 2) S. Yoshida, S. Hayano, J. Memb. Sci., 11, 157(1982). 3) J. D. Lamb, J. J. Christensen, J.
1) K. J. Laidler, "Reaction Kinetics", Vol. II, Pergamon Press, New York (1963) Chap. 1 ; P. G. Ashmore, "Catalysis and Inhibition of Chemical Reactio
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5) K. Irukayama, T. Kondo, F. Kai, M. Fujiki, Kuma. moto Med. J., 14, 157(1961). 6) K. Irukayama, M. Fujiki, F. Kai, T. Kondo, ibid., 15, 1(1962). 7)
5) K. Irukayama, T. Kondo, F. Kai, M. Fujiki, Kuma. moto Med. J., 14, 157(1961). 6) K. Irukayama, M. Fujiki, F. Kai, T. Kondo, ibid., 15, 1(1962). 7) K. Irukayama, F. Kai, M. Fujiki, T. Kondo, ibid., 15,
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