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Article

Synthesis, Characterization, and Coordination Chemistry of the 2-Azaphenalenyl Radical

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Shijun Zheng, Jie Lan, Saeed I. Khan, and Yves Rubin*

Contribution from the Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569

J. Am. Chem. Soc., 2003, 125 (19), pp 5786–5791

DOI: 10.1021/ja029236o

Publication Date (Web): April 19, 2003

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, rubin@chem.ucla.edu

Abstract

The 2-azaphenalenyl radical 2 has been synthesized and characterized by ESR spectroscopy. Variable-temperature ESR measurements were carried out on both the phenalenyl (1) and the 2-azaphenalenyl (2) radicals. The phenalenyl radical 1 has the known propensity to dimerize at temperatures below 20 °C, but unexpectedly less so than originally reported. The first experimental measurement of bond dissociation enthalpy for the dimerization of the phenalenyl radical 1 was obtained in CCl₄ (11.34 ± 0.11 kcal/mol) and toluene (9.8 ± 0.7 kcal/mol). The 2-azaphenalenyl radical 2 does not show a propensity to dimerize over the measurable temperature range (220−330 K), but does so in the presence of Cu(hfac)₂ (hfac = hexafluoroacetylacetonate). The latter complex was characterized by X-ray crystallography.

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Published In Issue May 14, 2003
Received November 6, 2002

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Article

Synthesis, Characterization, and Coordination Chemistry of the 2-Azaphenalenyl Radical