Organometallics
Communication
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Having identified active Fe(II) catalysts, future work will
probe mechanistic details. The electrophilic intermediate
derived from 1Fe may be an imidoiron(IV) complex. Authentic
imidoiron(IV) complexes are known; however, these were not
shown to effect CC aziridination or C−H aminations.17 One
unique example, a spin- and valence-isomeric Fe(III)-imido
radical formed by p-tBu-C6H4N3 activation at a three-
coordinate Fe(II) complex, reacts with toluene to yield the
benzylamine.5h Of particular interest are factors that discrim-
inate between radicaloid and electrophilic substrate additions
(Scheme 1), leading to the unique reactivity of 1Fe.
ASSOCIATED CONTENT
* Supporting Information
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S
Text, tables, and figures giving experimental details and NMR
characterization data for the organic products. This material is
́
(8) (a) Dıaz-Requejo, M. M.; Per
J. L. Organometallics 1997, 16, 4399−4402. (b) Dıaz-Requejo, M. M.;
Belderraín, T. R.; Nicasio, M. C.; Trofimenko, S.; Perez, P. J. J. Am.
Chem. Soc. 2003, 125, 12078−12079. (c) Mairena, M. A.; Dıaz-
́
ez, P. J.; Brookhart, M.; Templeton,
́
́
AUTHOR INFORMATION
Corresponding Author
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Requejo, M. M.; Belderraın, T. R.; Nicasio, M. C.; Trofimenko, S.;
Perez, P. J. Organometallics 2004, 23, 253−256. (d) Fructos, M. R.;
Trofimenko, S.; Dıaz-Requejo, M. M.; Per
2006, 128, 11784−11791. (e) Cano, I.; Nicasio, M. C.; Per
́
́
́
ez, P. J. J. Am. Chem. Soc.
ez, P. J.
Notes
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The authors declare no competing financial interest.
́
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Dalton Trans. 2009, 730−734. (f) Fuentes, M. A.; Alvarez, E.;
Caballero, A.; Perez, P. J. Organometallics 2012, 31, 959−965.
́
ACKNOWLEDGMENTS
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(9) Trofimenko, S. J. Am. Chem. Soc. 1970, 92, 5118−5126.
(10) Trofimenko, S. Chem. Rev. 1993, 93, 943−980.
(11) Yamada, Y.; Yamamoto, T.; Okawara, M. Chem. Lett. 1975,
361−362.
We acknowledge the donors of the American Chemical Society
Petroleum Research Fund (49296-DNI3) for support of this
research. We thank Prof. Stephen C. Bergmeier and Ms. Fang
Fang for helpful discussions.
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dx.doi.org/10.1021/om3009102 | Organometallics XXXX, XXX, XXX−XXX