Advertisement

Applied Magnetic Resonance

, 36:9 | Cite as

Synthesis, Characterization and Reactivity Study of a New Penta-Coordinated Mn(II) Complex

  • Gustav Berggren
  • Ping Huang
  • Lars Eriksson
  • Magnus F. AnderlundEmail author
Article

Abstract

A penta-coordinated Mn(II) compound [dqpMnCl2] (1) (dqp = 2,6-di-(8-quinoline-yl)-pyridine) has been synthesized and its X-ray crystallographic structure is reported here. Magnetic susceptibility measurements confirmed a high-spin Mn(II) (S = 5/2) center in 1. The X-band EPR spectrum of 1 in dimethylformamide solution exhibits widely distributed transitions in the spectral range from 0 to 700 mT with particularly well-resolved hyperfine lines due to the 55Mn (I = 5/2) nucleus. The abundance of highly resolved transition lines in the spectrum facilitated the electron paramagnetic resonance spectral simulation which revealed large zero-field splitting and g-anisotropies. When dissolved, 1 exists in equilibrium with a hexa-coordinated species, the latter probably resulting from disassociation of one chlorido-ligand allowing ligation of two solvent molecules. The redox behavior of 1 was studied and was compared to that of a structural analog for which water oxidation in the presence of a chemical oxidant has been shown. The results from water oxidation trials of 1 are discussed.

Keywords

Hyperfine Coupling Water Oxidation Mn4Ca Cluster Bulk Electrolysis Solid State Spectrum 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgments

The authors wish to thank Dr. Olof Johansson and Michael Jäger for providing the dqp-ligand. The authors would like to express their great gratitude to the financial support from the Swedish Energy Agency, the Knut and Alice Wallenberg Foundation, the EU/NEST Projects SOLAR-H (contract # 516510) and the EU/Energy project SOLAR-H2 (contract #2 12508).

References

  1. 1.
    B. Loll, J. Kern, W. Saenger, A. Zouni, J. Biesiadka, Nature 438, 1040–1044 (2005)CrossRefADSGoogle Scholar
  2. 2.
    M. Haumann, C. Muller, P. Liebisch, L. Iuzzolino, J. Dittmer, M. Grabolle, T. Neisius, W. Meyer-Klaucke, H. Dau, Biochemistry 44, 1894–1908 (2005)CrossRefGoogle Scholar
  3. 3.
    J. Messinger, Phys. Chem. Chem. Phys. 6, E11–E12 (2004)CrossRefGoogle Scholar
  4. 4.
    K.N. Ferreira, T.M. Iverson, K. Maghlaoui, J. Barber, S. Iwata, Science 303, 1831–1838 (2004)CrossRefADSGoogle Scholar
  5. 5.
    C. Goussias, A. Boussac, A.W. Rutherford, Philos. T. Roy. Soc. B 357, 1369–1381 (2002)CrossRefGoogle Scholar
  6. 6.
    J.H.A. Nugent, A.M. Rich, M.C.W. Evans, Biochim. Biophys. Acta Bioenerg. 1503, 138–146 (2001)CrossRefGoogle Scholar
  7. 7.
    J.P. McEvoy, G.W. Brudvig, Chem. Rev. 106, 4455–4483 (2006)CrossRefGoogle Scholar
  8. 8.
    H.Y. Chen, R. Tagore, G. Olack, J.S. Vrettos, T.C. Weng, J. Penner-Hahn, R.H. Crabtree, G.W. Brudvig, Inorg. Chem. 46, 34–43 (2007)CrossRefGoogle Scholar
  9. 9.
    H. Chen, R. Tagore, S. Das, C. Incarvito, J.W. Faller, R.H. Crabtree, G.W. Brudvig, Inorg. Chem. 44, 7661–7670 (2005)CrossRefGoogle Scholar
  10. 10.
    M. Yagi, K. Narita, J. Am. Chem. Soc. 126, 8084–8085 (2004)CrossRefGoogle Scholar
  11. 11.
    J. Limburg, J.S. Vrettos, L.M. Liable-Sands, A.L. Rheingold, R.H. Crabtree, G.W. Brudvig, Science 283, 1524–1527 (1999)CrossRefADSGoogle Scholar
  12. 12.
    C. Baffert, S. Romain, A. Richardot, J.C. Lepretre, B. Lefebvre, A. Deronzier, M.N. Collomb, J. Am. Chem. Soc. 127, 13694–13704 (2005)CrossRefGoogle Scholar
  13. 13.
    H.Y. Chen, J.W. Faller, R.H. Crabtree, G.W. Brudvig, J. Am. Chem. Soc. 126, 7345–7349 (2004)CrossRefGoogle Scholar
  14. 14.
    J. Limburg, J.S. Vrettos, H.Y. Chen, J.C. de Paula, R.H. Crabtree, G.W. Brudvig, J. Am. Chem. Soc. 123, 423–430 (2001)CrossRefGoogle Scholar
  15. 15.
    R. Tagore, H. Chen, H. Zhang, R.H. Crabtree, G.W. Brudvig, Inorg. Chim. Acta 360, 2983–2989 (2007)CrossRefGoogle Scholar
  16. 16.
    R. Tagore, H.Y. Chen, R.H. Crabtree, G.W. Brudvig, J. Am. Chem. Soc. 128, 9457–9465 (2006)CrossRefGoogle Scholar
  17. 17.
    M. Abrahamsson, M. Jager, T. Osterman, L. Eriksson, P. Persson, H.C. Becker, O. Johansson, L. Hammarstrom, J. Am. Chem. Soc. 128, 12616–12617 (2006)CrossRefGoogle Scholar
  18. 18.
    G.M. Sheldrick, SHELXS97 and SHELXL97 (University of Göttingen, Göttingen, 1997)Google Scholar
  19. 19.
    C. Mantel, C. Baffert, I. Romero, A. Deronzier, J. Pecaut, M.N. Collomb, C. Duboc, Inorg. Chem. 43, 6455–6463 (2004)CrossRefGoogle Scholar
  20. 20.
    J.R. Pilbrow, Transition Ion Electron Paramagnetic Resonance (Oxford University Press, New York, 1991)Google Scholar
  21. 21.
    F.E. Mabbs, D. Collison, Electron Paramagnetic Resonance of d Transition Metal Compounds (Studies in Inorganic Chemistry) (Elsevier, Amsterdam, 1992)Google Scholar
  22. 22.
    C. Baffert, M.N. Collomb, A. Deronzier, S. Kjaergaard-Knudsen, J.M. Latour, K.H. Lund, C.J. McKenzie, M. Mortensen, L. Nielsen, N. Thorup, Dalton Trans. 1765–1772 (2003)Google Scholar
  23. 23.
    C. Bucher, E. Duval, J.M. Barbe, J.N. Verpeaux, C. Amatore, R. Guilard, L. Le Pape, J.M. Latour, S. Dahaoui, C. Lecomte, Inorg. Chem. 40, 5722–5726 (2001)CrossRefGoogle Scholar
  24. 24.
    C. Duboc, V. Astier-Perret, H.Y. Chen, J. Pecaut, R.H. Crabtree, G.W. Brudvig, M.N. Collomb, Inorg. Chim. Acta 359, 1541–1548 (2006)CrossRefGoogle Scholar
  25. 25.
    S. Un, L.C. Tabares, N. Cortez, B.Y. Hiraoka, F. Yamakura, J. Am. Chem. Soc. 126, 2720–2726 (2004)CrossRefGoogle Scholar
  26. 26.
    W.C. Stalling, K.A. Pattridge, M.L. Ludwig, Superoxide and Superoxide Dismutase in Chemistry, Biology and Medicine (Elsevier, Amsterdam, 1986)Google Scholar
  27. 27.
    O. Kahn, Molecular Magnetism (Wiley-VCH, New York, 1993)Google Scholar
  28. 28.
    P. Kurz, G. Berggren, M.F. Anderlund, S. Styring, Dalton Trans. 4258–4261 (2007)Google Scholar

Copyright information

© Springer 2009

Authors and Affiliations

  • Gustav Berggren
    • 1
  • Ping Huang
    • 1
  • Lars Eriksson
    • 2
  • Magnus F. Anderlund
    • 1
    Email author
  1. 1.Department of Photochemistry and Molecular Science, Ångström LaboratoryUppsala UniversityUppsalaSweden
  2. 2.Division of Structural Chemistry, Arrhenius LaboratoryStockholm UniversityStockholmSweden

Personalised recommendations