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Catalytic N−N Coupling of Aryl Azides To Yield Azoarenes via Trigonal Bipyramid Iron−Nitrene Intermediates

Mankad, Neal P. and Müller, Peter and Peters, Jonas C. (2010) Catalytic N−N Coupling of Aryl Azides To Yield Azoarenes via Trigonal Bipyramid Iron−Nitrene Intermediates. Journal of the American Chemical Society, 132 (12). pp. 4083-4085. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20141209-131428584

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Abstract

The reactivity of the trigonal bipyramidal iron(I) complex [SiP^(iPr)_3]Fe(N_2) ([SiP^(iPr)_3] = (2-iPr_2PC_6H_4)_3Si−) toward organoazides has been examined. 1-Adamantylazide was found to coordinate the iron center to form stable [SiP^(iPr)_3]Fe(η^1-N_3Ad). Aryl azides instead afforded unstable [SiP^(iPr)_3]Fe(N_3Ar) species that decayed gradually to regenerate [SiP^(iPr)_3]Fe(N_2) with release of azoarenes (ArN═NAr). The conversion of aryl azides to azoarenes can thus be achieved catalytically. Competitive trapping experiments strongly suggest the intermediacy of reactive nitrene complexes of the type [SiP^(iPr)_3]Fe(NAr) that couple bimolecularly in the N−N bond forming step. Evidence for one such intermediate was provided by electron paramagnetic resonance spectroscopy via photolysis of [SiP^(iPr)_3]Fe(N_3Ar) in a frozen glass. The electronic structures of these putative nitrene intermediates have been examined by DFT methods.


Item Type:Article
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http://10.1021/ja910224cDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja910224cPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja910224cPublisherSupporting Information
Additional Information:© 2010 American Chemical Society Received December 3, 2009. Publication Date (Web): March 3, 2010. This work was funded by the NIH (GM-070757). Tim Kowalczyk and Prof. Seth Brown provided helpful discussions.
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NIHGM-070757
Record Number:CaltechAUTHORS:20141209-131428584
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20141209-131428584
Official Citation:Catalytic N−N Coupling of Aryl Azides To Yield Azoarenes via Trigonal Bipyramid Iron−Nitrene Intermediates Neal P. Mankad, Peter Müller, and Jonas C. Peters Journal of the American Chemical Society 2010 132 (12), 4083-4085
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52505
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:09 Dec 2014 21:28
Last Modified:09 Dec 2014 21:28

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