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Synfacts 2006(12): 1229-1229  
DOI: 10.1055/s-2006-955582
Synthesis of Materials and Unnatural Products
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Biradicaloid Character of Doubly Linked Corrole Dimers

Contributor(s): Timothy M. Swager, Mark S. Taylor
S. Hiroto, K. Furukawa, H. Shinokubo*, A. Osuka*
Kyoto University, CREST & PRESTO, Japan Science and Technology Agency and Institute for Molecular Science, Okazaki, Japan
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Publication History

Publication Date:
22 November 2006 (online)

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Significance

The synthesis and properties of a corrole dimer linked through a cyclooctatetraene-like central ring system are presented. Palladium-catalyzed oxidative dimerization of pinacolboro­nate 1 was followed by dehydrogenation with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) to yield the doubly linked bis(corrole) in its oxidized form 2. Treatment of 2 with sodium borohydride generated the reduced form 3. Compounds 2 and 3 were metallated with zinc(II) and cobalt(III), respectively. The electrochemical behavior, ESR spectrum, and temperature-dependent magnetic susceptibility of the 2-Zn complex demonstrated that this species exhibits substantial singlet biradical character, a conclusion that was supported by computational studies.