Halobenzenes and Ir(I): Kinetic C−H Oxidative Addition and Thermodynamic C−Hal Oxidative Addition
2005; American Chemical Society; Volume: 127; Issue: 48 Linguagem: Inglês
10.1021/ja0557637
ISSN1943-2984
AutoresLei Fan, Sean Parkin, Oleg V. Ozerov,
Tópico(s)Oxidative Organic Chemistry Reactions
ResumoA (PNP)Ir fragment undergoes facile, room-temperature oxidative addition of C-H bonds in arenes and haloarenes in preference to aromatic carbon-halogen bonds. This preference, however, is determined to be kinetic in nature. Oxidative addition of C-Cl and C-Br is preferred thermodynamically. The products of the C-Cl or C-Br oxidative addition are separated from the C-H oxidative addition products by a high activation barrier and are only accessible at >100 degrees C. Of the C-H oxidative addition products of chlorobenzene, the isomer with the o-ClC6H4 ligand has the lowest energy.
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