Alec H. Christian, P. Müller, Sebastien Monfette
Apr 18, 2014
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0
Influential Citations
32
Citations
Journal
Organometallics
Abstract
The synthesis, characterization, and reactivity of intermediates formed in the Ni-catalyzed Suzuki–Miyaura cross-coupling (SMC) of an aryl chloride are described. Oxidative addition of 1-chloro-4-trifluoromethylbenzene (1) to a mixture of Ni(cod)2 and PCy3 afforded NiCl(4-CF3Ph)(PCy3)2 (2), which then cleanly provided dimeric [Ni(4-CF3Ph)(μ–OH)(PCy3)]2 (3) by reaction with aqueous KOH. Reactivity studies of 2 and 3 with phenylboronic acid (4) revealed that, while 2 affords only traces of the biphenyl coupling product after 24 h, the same reaction with 3 is complete within minutes at room temperature. In contrast, the reaction of 3 with potassium phenyltrihydroxyborate (6) is much slower than that with boronic acid 4, and significantly lower yields of the cross-coupling product are obtained. We show that formation of the hydroxo species 3 is the rate-determining step in the present SMC.