Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

A New Model for the Reduced Form of Purple Acid Phosphatase: Structure and Properties of $[Fe_2BPLMP(OAc)_2](BPh_4)_2$

  • Published : 1998.06.20
Download PDF
⟨ Previous Next ⟩

Abstract

$[Fe^{II}Fe^{III}BPLMP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)amino) methyl]-4-methylphenol (HBPLMP). Complex I has been characterized by X-ray diffraction method as having (μ-phenoxo)bis(acetato)diiron core. Complex 1 was crystallized in the monoclinic space group C2/c with the following cell parameters: a=41.620(6) Å, b=14.020(3) Å, c=27.007(4) Å, β=90.60(2)°, and Z=8. The iron centers in the complex 1 are ordered as indicated by the difference in the Fe-O bond lengths which match well with typical $Fe^{III}-O\; and\; Fe^{II}-O$ bond lengths. Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electochemical methods. Complex 1 exhibits strong bands at 592 nm, 1380 nm in $CH_3CN$ (ε = 1.0 × 103 , 3.0 × 102). These are assigned to $phenolate-to-Fe^{III}$ and intervalence charge-transfer transitions, respectively. Its NMR spectrum exhibits sharp isotropically shifted resonances, which number half of those expected for a valence-trapped species, indicating that electron transfer between $Fe^{II}\;and\;Fe^{III}$ centers is faster than NMR time scale. This complex undergoes quasireversible one-electron redox processes. The $Fe^{III}_2/Fe^{II}Fe^{III}\;and\;Fe^{II}Fe^{III}/Fe^{II}_2$ redox couples are at 0.655 and -0.085 V vs SCE, respectively. It has $K_{comp}=3.3{\times}10^{12}$ representing that BPLMP/bis(acetate) ligand combination stabilizes a mixed-valence $Fe^{II}Fe^{III}$ complex in the air. Complex 1 exhibits a broad EPR signal centered near g=1.55 which is a characteristic feature of the antiferromagnetically coupled high-spin $Fe^{II}Fe^{III}$ system $(S_{total}=1/2)$. This is consistent with the magnetic susceptibility study showing the weak antiferromagnetic coupling $(J= - 4.6\;cm^{-1},\; H= - 2JS_1{\cdot}S2)$ between $Fe^{II}\; and \;Fe^{III}$center.

Keywords

References

  1. in Iron Carriers and Iron Proteins v.5 Sanders-Loehr, J.;Loehr, T. M.(ed.)
  2. Prog. Inorg. Chem. v.38 Que, L., Jr.;Ture, A. E.
  3. Chem. Rev. v.90 Vincent, J. B.;Oliver-Lilly, G.L.;Averill, B. A.
  4. Advances, in Inorganic Chemistry v.43 Anderson, K. K.;Gruslund, A.
  5. Chem. Rev. v.96 Wilcox, D. E.
  6. Biochemistry v.20 Davis, J. C.;Lin, S. S.;Averill, B. A.
  7. J. Biol. Chem. v.257 Antanaitis, B. C.;Aisen, P.
  8. Adv. Inorg, Biochem. v.5 Antanaitis, B. C.;Aisen, P.
  9. J. Biol. Chem. v.257 Antannaitis, B. C.;Strekas, T.;Aisen, P.
  10. J. Am. chem. Soc. v.109 Averill, B. A.;Davis, J. C.;Burman, S.;Zirino, T.;Sanders-Loehr, J.;Loehr, T. M.;Sage, J. T.;Debrunner, P. G.
  11. Eur. J. Biochem. v.199 Dietrich. M.;Munsternmann, D.;Suerbaum, H.;Wizel, H.
  12. Inorg. Chem. v.25 Kauzlarich, S. M.;Teo, B. K.;Zirino, T.;Burman, S.;Davis, J. C.;Averill, B. A.
  13. Biochemistry v.31 Crowder, M. W.;Vincent, J. B.;Averill. B. A.
  14. J. Biol. Chem. v.259 Antanatitis, B. C.;Aisen, P.
  15. Inorg. Chem. v.35 Lim, J. S.;Manuel, A. S.;Sykes, A. G.
  16. J. Biol. Chem. v.258 Antanaitis, B. C.;aisen, P,;Lilienthal, H. R.
  17. J. Am. Chem. Soc. v.112 Davis, S. S.;Que, L., Jr.
  18. J. Biol. Chem. v.261 Pyrz, J. W.;Sage, J. T.;Debrunner, P. G.;Que, L., Jr.
  19. J. Biol. Chem. v.263 Day, E. P.;David, S. S.;Peterson, J.;Dunham, W. R.;Bonvoison, J. J.;Sands, R. H.;Que, L., Jr.
  20. J. Am. Chem. v.115 True, A. E.;Scarrow, R. C.;Randall, C. R.;Holz, R. C.;Que, L., Jr.
  21. J. Biol. Chem. v.258 Lauffer, R. B.;antanaitis, B. C.;Aisen, P.;Que, L., Jr.
  22. J. Am. Chem. v.112 Sarrow, R. C.;Pyrz, J. W.;Que, L.; Jr.
  23. Biochemistry v.31 Wang, Z.;Ming, L. J.;Que, L., Jr.
  24. Biochemistry v.31 Crans, D. C.;Simone, S. M.;Holz, R. C.;Que, L., Jr.
  25. Science v.268 Strater, N.;Klabund, T.;Tuker, P.;Witzel, H.;Krebs, B.
  26. Nature v.345 Nordlund, P.;Sjoberg, B. M.;Eklund, H.
  27. Chem. Rev. v.96 Wallar, B. J.;Lipscomb, J. D.
  28. Bull. Chem. Soc. Jpn. v.60 Suzuki, M.;Uehara, A.;Oshio, H.;Endo, K.;Yanaga, M.;Kida, S.;Saito, K.
  29. J. Am. Chem. Soc. v.110 Borovik, A. S.;Que, L., Jr.
  30. J. Am. Chem. Soc. v.111 Borovik, A. S.;Papaefthymiou, V.;Taylor, L. F.;Anderson, O. P.;Que, L., Jr.
  31. J. Am. Chem. Soc. v.114 Mashuta, M. S.;Webb, R. J.;msCusker, J. K.;Schmin, E. A.;Oberhausen, k. J.;Richardson, J. F.;Buchanan, R. M.;Hendrikson, D. N.
  32. J. Am. Chem. Soc. v.111 Mashuta, M. S.;Webb, R. J.;Oserhausen, K. J.;Richardson, J. F.;Buchanan, R. M.;Hendrickson, D. N.
  33. Bull. Chem. Soc. Jpn. v.61 Suzuki, M.;Oshio, H.;Uehara, A.;Endo, K.;Yanaga, M.;Kida, S.;Saito, K.
  34. J. Am. Chem. Soc. v.109 Borovik, A. S.;Murch, B. P.;Que, L., Jr.Papaefthymiou, V.;Munck, E.
  35. Inorg.Chim. Acta. v.197 Neves, A.;Erthal, S. M. D.;Drago, V.;Griesar, K.;Haase, W.
  36. Inorg. Chem. v.35 Neves, A.;de Brito, M. A.;Vencato, I.;Drago, V.;Griesar, K.;Haase, W.;Mascarenhas, Y. P.
  37. Inorg. Chim. Acta. v.214 Neves, A.;de Brito, M. A.;Vencato, I.;Drago, V.;Griesar, K.;Haase, W.
  38. Inorg. Chim. Acta. v.237 Neves, A.;de Brito, M. A.;Drago, V.;Griesar, K.;Haasr, W.
  39. Inorg. Chem. v.33 Krebs, B.;Schepers, K.;Bremer, B.;Henkel, G.;Althaus, E.;Muller-Warmuth, W.;Griesar, K.;Haase, W.
  40. Inorg, Chem. v.34 Nie, H.;Aubin, S. M.;Mashuta, M. S.;Wu, C. C.;Richardson, J. F.;Hendrickson, D. N.;Buchanan, R. M.
  41. J. Am. Chem. Soc. v.119 Zang, Y.;Kim, J.;Dong, Y.;Wilkinson, E. C.;Appelman, E. H.;Que, L., Jr.
  42. Inorg. Chem. v.31 Ming, L. J.;Jang, H. G.;Que, L., Jr.
  43. NMR of Paramagnetic Moleeules in Biological Systems Bertini, I.;Luchinat, C.
  44. Adv. Inorg. Chem. and Radio-chem v.10 Robin, M. B.;Day, P.
  45. Prog. Inorg. Chem. v.30 Creutz, C.
  46. J. Am. Chem. Soc. v.103 Gagne, R. R.;Spiro, C. L.;Smith, T. J.;Hamann, C. A.;Thies, W. R.;Shuemke, A. K.
  47. in Electron Spin Resonance Elementary Theory and Practical Applications Wertz, J. E.;Bolton, J. R.
  48. Biochemistry v.11 Munck, E.;Debrunner, P. G.;Tsibris, J. C. M.;Gunsalus, I. C.
  49. Biophys. J. v.52 Day, E. P.;Kent, T. A.;Lindahl, P. A.;Munck, E.;Orme-Johnson, W. H.;Roder, H.;Roy, A.