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High- and Low-Valent tris-N-Heterocyclic Carbene Iron Complexes pp 101–118Cite as

PhB(tBuIm) ?3 : Synthesis, Structure, and Reactivity of an Iron(V) Nitride

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Abstract

High-valent iron species are proposed as active intermediates in the cycles of many important biocatalysts. Iron(IV) is the most readily accessible high oxidation state, although iron(V) has also been proposed as a key intermediate in some non-heme dioxygenases. Structural and spectroscopic precedent for these intermediates has often come from studies of well-defined model complexes. For example, the iron(IV) oxo moiety, which has long been known to be at the catalytic centers of oxygenases, was first crystallographically characterized in an octahedral iron complex of an N-methylated 1,4,8,11-tetraazacyclotetradecane (cyclam) macrocycle .Similar cyclam derivatives have also allowed for the preparation and detailed spectroscopic characterization of octahedral Fe(V) and Fe(VI) nitrido complexes, but the structural characterization and reactivity of these fleeting intermediates, which are usually studied at low temperatures in frozen matrices, remains elusive.

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References

  1. K. Chen, M. Costas, J. Kim, A.K. Tipton, L. Que, J. Am. Chem. Soc. 124, 3026 (2002)

    Article  CAS  Google Scholar 

  2. M. Costas, M.P. Mehn, M.P. Jensen, L. Que Jr., Chem. Rev. 104, 939 (2004)

    Article  CAS  Google Scholar 

  3. J.-U. Rohde, J.-H. In, M.H. Lim, W.W. Brennessel, M.R. Bukowski, A. Stubna, E. Münck, W. Nam, L. Que, Science 299, 1037 (2003)

    Article  CAS  Google Scholar 

  4. M. Aliaga-Alcalde, S.D. George, B. Mienert, E. Bill, K. Wieghardt, F. Neese, Angew. Chem. 117, 2968 (2005)

    Article  Google Scholar 

  5. J.F. Berry, E. Bill, E. Bothe, S.D. George, B. Mienert, F. Neese, K. Wieghardt, Science 312, 1937 (2006)

    Article  CAS  Google Scholar 

  6. G. Ertl, Chem. Rec. 1, 33 (2001)

    Article  CAS  Google Scholar 

  7. B.M. Hoffman, D.R. Dean, L.C. Seefeldt, Acc. Chem. Res. 42, 609 (2009)

    Article  CAS  Google Scholar 

  8. M.P. Hendrich, W. Gunderson, R.K. Behan, M.T. Green, M.P. Mehn, T.A. Betley, C.C. Lu, J.C. Peters, Proc. Natl. Acad. Sci. 103, 17107 (2006)

    Article  CAS  Google Scholar 

  9. G. Ertl, Angew. Chem. Int. Ed. 29, 1219 (1990)

    Article  Google Scholar 

  10. O. Einsle, F.A. Tezcan, S.L.A. Andrade, B. Schmid, M. Yoshida, J.B. Howard, D.C. Rees, Science 297, 1696 (2002)

    Article  CAS  Google Scholar 

  11. T.-C. Yang, N.K. Maeser, M. Laryukhin, H.-I. Lee, D.R. Dean, L.C. Seefeldt, B.M. Hoffman, J. Am. Chem. Soc. 127, 12804 (2005)

    Article  CAS  Google Scholar 

  12. D. Lukoyanov, V. Pelmenschikov, N. Maeser, M. Laryukhin, T.-C. Yang, L. Noodleman, D.R. Dean, D.A. Case, L.C. Seefeldt, B.M. Hoffman, Inorg. Chem. 46, 11437 (2007)

    Article  CAS  Google Scholar 

  13. T.A. Betley, J.C. Peters, J. Am. Chem. Soc. 126, 6252 (2004)

    Article  CAS  Google Scholar 

  14. C. Vogel, F.W. Heinemann, J. Sutter, C. Anthon, K. Meyer, Angew. Chem. Int. Ed. 47, 2681 (2008)

    Article  CAS  Google Scholar 

  15. J.J. Scepaniak, M.D. Fulton, R.P. Bontchev, E.N. Duesler, M.L. Kirk, J.M. Smith, J. Am. Chem. Soc. 130, 10515 (2008)

    Article  CAS  Google Scholar 

  16. J.J. Scepaniak, C.S. Vogel, M.M. Khusniyarov, F.W. Heinemann, K. Meyer, J.M. Smith, Science 331, 1049 (2011)

    Article  CAS  Google Scholar 

  17. T.A. Jackson, J.-U. Rohde, M.S. Seo, C.V. Sastri, R. DeHont, A. Stubna, T. Ohta, T. Kitagawa, E. Münck, W. Nam, J. Lawrence Que, J. Am. Chem. Soc, 130,12394 (2008)

    Google Scholar 

  18. C.E. Schulz, P. Nyman, P.G. Debrunner, J. Chem. Phys. 87, 5077 (1987)

    Article  CAS  Google Scholar 

  19. R.H. Herber, Chemical Mössbauer Spectroscopy (Plenum Press, New York, 1984)

    Book  Google Scholar 

  20. A.A. Yousif, H. Winkler, H. Toftlund, A.X. Trautwein, R.H. Herber, J. Phys.: Condens. Matter 1, 7103 (1989)

    CAS  Google Scholar 

  21. K. Meyer, E. Bill, B. Mienert, T. Weyhermüller, K. Wieghardt, J. Am. Chem. Soc. 121, 4859 (1999)

    Article  CAS  Google Scholar 

  22. F.T. de Oliveira, A. Chanda, D. Banerjee, X. Shan, S. Mondal, L. Que Jr., E.L. Bominaar, E. Münck, T.J. Collins, Science 315, 835 (2007)

    Article  Google Scholar 

  23. M. Berthelot, Rep. Chim. Appl. 1, 284 (1859)

    Google Scholar 

  24. J.L. Bras, H. Jiao, W.E. Meyer, F. Hampel, J.A. Gladysz, J. Organomet. Chem. 616, 54 (2000)

    Article  Google Scholar 

  25. F. Neese, ORCA — an Ab Initio, Density Functional and Semiempirical SCF-MO Package, version 2.7 revision 0 (Institut für Physikalische und Theoretische Chemie Universität Bonn, Germany, 2009)

    Google Scholar 

  26. A.D. Becke, Phys. Rev. A 38, 3098 (1988)

    Article  CAS  Google Scholar 

  27. J.P. Perdew, Phys. Rev. B 34, 7406 (1986)

    Article  Google Scholar 

  28. A.D. Becke, J. Chem. Phys. 98, 5648 (1993)

    Article  CAS  Google Scholar 

  29. A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 97, 2571 (1992)

    Article  Google Scholar 

  30. S. Sinnecker, L.D. Slep, E. Bill, F. Neese, Inorg. Chem. 44, 2245 (2005)

    Article  CAS  Google Scholar 

  31. F. Neese, Inorg. Chim. Acta 337, 181 (2002)

    Article  Google Scholar 

  32. This basis is based on the TurboMole DZ basis, developed by Ahlrichs and coworkers and obtained from the basis set library under ftp://chemie.uni-karlsruhe.de/pub/basen

  33. A. Klamt, G. Schürmann, J Chem Soc, Perkin Trans 799 (1993)

    Google Scholar 

  34. C. van Wüllen, J. Chem. Phys. 109, 392 (1998)

    Article  Google Scholar 

  35. S. Portmann, Molekel, version 4.3.win32 (CSCS/UNI Geneva, Switzerland, 2002)

    Google Scholar 

  36. A.L. Chaney, E.P. Marbach, Clin. Chem. 8, 130 (1962)

    CAS  Google Scholar 

  37. M.W. Weatherburn, Anal. Chem. 39, 971 (1967)

    Article  CAS  Google Scholar 

  38. SADABS 2008/1; Bruker AXS, Inc. (2008)

    Google Scholar 

  39. SHELXTL NT 6.12; Bruker AXS, Inc. (2002)

    Google Scholar 

Download references

Acknowledgments

Text, schemes, and figures of this chapter, in part, are reprints of the materials published in [16]. The dissertation author was the secondary researcher and author. The co-authors listed in the publication also participated in the research. The permission to reproduce the paper was granted by the American Association for the Advancement of Science. Copyright 2011, American Association for the Advancement of Science.

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  1. Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstraße 1, 91058, Erlangen, Germany

    Carola S. Vogel

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Vogel, C.S. (2012). PhB(tBuIm) ?3 : Synthesis, Structure, and Reactivity of an Iron(V) Nitride. In: High- and Low-Valent tris-N-Heterocyclic Carbene Iron Complexes. Springer Theses. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-27254-7_5

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