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Atom-Transfer Radical Addition Reactions Catalyzed by RuCp* Complexes: A Mechanistic Study

✍ Scribed by Mariano A. Fernández-Zúmel; Katrin Thommes; Gregor Kiefer; Andrzej Sienkiewicz; Katarzyna Pierzchala; Kay Severin

Publisher
John Wiley and Sons
Year
2009
Tongue
English
Weight
378 KB
Volume
15
Category
Article
ISSN
0947-6539

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✦ Synopsis

Abstract

Kinetic and spectroscopic analyses were performed to gain information about the mechanism of atom‐transfer radical reactions catalyzed by the complexes [RuCl~2~Cp*(PPh~3~)] and [RuClCp*(PPh~3~)~2~] (Cp*=pentamethylcyclopentadienyl), in the presence and in the absence of the reducing agent magnesium. The reactions of styrene with ethyl trichloroacetate, ethyl dichloroacetate, or dichloroacetonitrile were used as test reactions. The results show that for substrates with high intrinsic reactivity, such as ethyl trichloroacetate, the oxidation state of the catalyst in the resting state is +3, and that the reaction is zero‐order with respect to the halogenated compound. Furthermore, the kinetic data suggest that the metal catalyst is not directly involved in the rate‐limiting step of the reaction.

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