Communication

A Two-State Reactivity Model Explains Unusual Kinetic Isotope Effect Patterns in C[BOND]H Bond Cleavage by Nonheme Oxoiron(IV) Complexes†

  1. Eric J. Klinker Dr.2,
  2. Sason Shaik Prof. Dr.1,
  3. Hajime Hirao Dr.1,
  4. Lawrence Que Jr. Prof. Dr.2

Article first published online: 7 JAN 2009

DOI: 10.1002/anie.200804029

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 48, Issue 7, pages 1291–1295, February 2, 2009

Additional Information

How to Cite

Klinker, Eric J., Shaik, S., Hirao, H. and Que, L. (2009), A Two-State Reactivity Model Explains Unusual Kinetic Isotope Effect Patterns in C[BOND]H Bond Cleavage by Nonheme Oxoiron(IV) Complexes. Angew. Chem. Int. Ed., 48: 1291–1295. doi: 10.1002/anie.200804029

Author Information

  1. 1

    Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel), Fax: (+972) 2-658-4680

  2. 2

    Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455 (USA), Fax: (+1) 612-624-7029

  1. †

    We thank the National Institutes of Health (GM-33162 to L.Q.), the University of Minnesota Graduate School (dissertation fellowship to E.J.K.), the Ministry of Education and Research within the Framework of the German–Israeli Project Cooperation (DIP; to S.S.), and the JSPS Postdoctoral Fellowship for Research Abroad (to H.H.) for support of this research.

Publication History

  1. Issue published online: 28 JAN 2009
  2. Article first published online: 7 JAN 2009
  3. Manuscript Revised: 12 DEC 2008
  4. Manuscript Received: 14 AUG 2008

Funded by

  • National Institutes of Health. Grant Number: GM-33162
  • University of Minnesota Graduate School
  • Ministry of Education and Research
  • German–Israeli Project Cooperation
  • JSPS Postdoctoral Fellowship for Research Abroad

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Keywords:

  • bioinorganic chemistry;
  • iron;
  • isotope effects;
  • isotopic labeling;
  • two-state reactivity

Abstract

Thumbnail image of graphical abstract

It's in the bond: The cleavage of C[BOND]H bonds by two related oxoiron(IV) complexes shows a range of kinetic isotope effect (KIE) values that exhibit an unusual dependence on the C[BOND]H bond strength. Large nonclassical KIEs are observed for bond strengths below 93 kcal mol−1, while semiclassical values are found above this value (see graph, DHA=9,10-dihydroanthracene). This nonintuitive behavior can be rationalized by invoking a two-state reactivity model.

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