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Autocatalytic intermolecular versus intramolecular deprotonation in C-H bond activation of functionalized arenes by ruthenium(II) or palladium(II) complexes.

Abstract : The activation of the C-H bond of 1-phenylpyrazole (2) and 2-phenyl-2-oxazoline (3) by [Ru(OAc)2(p-cymene)] is an autocatalytic process catalyzed by the co-product HOAc. The reactions are indeed faster in the presence of acetic acid and water but slower in the presence of a base K2CO3. A reactivity order is established in the absence of additives: 2-phenylpyridine>2-phenyl-2-oxazoline>1-phenylpyrazole (at RT). The accelerating effect of added acetate ions reveals an intermolecular deprotonation after C-H bond activation by a cationic Ru(II) center (SE 3 mechanism). The reactions of 1-phenylpyrazole and 2-phenyl-2-oxazoline first lead to the neutral cyclometalated complexes A2 and A3 ligated by one acetate. The latter dissociate to the cationic complexes B2(+) and B3(+), respectively, and acetate. A slow incorporation of one or two D atoms into 2, 3, and 2-phenylpyridine (1) was observed in the presence of deuterated acetic acid. The "reversibility" of the C-H bond activation/deprotonation takes place from the cationic complexes Bn(+) (n=1-3). They are also involved in oxidative additions to PhI, which are rate-determining and lead to the mono- and bis-phenylated products at high temperatures. A general mechanism is proposed for the arylation of arenes 1-3 catalyzed by [Ru(OAc)2(p-cymene)]. In contrast, the reaction of Pd(OAc)2 with 2-phenylpyridine (1), is much faster: Pd(OAc)2>[Ru(OAc)2(p-cymene)]. Since the kinetics is not affected by added acetates, the reaction proceeds through a CMD mechanism assisted by a ligated acetate (intramolecular process) and is irreversible. A bis-cyclometalated Pd(II)^Pd(II) dimer D'1 is formed whose bielectronic electrochemical oxidation leads to a [Pd(III)^Pd(III)](2+) dimer, in agreement with the result of a reported chemical oxidation used in arene functionalizations catalyzed by Pd(OAc)2.
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https://hal.archives-ouvertes.fr/hal-00879895
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Submitted on : Tuesday, November 5, 2013 - 9:54:02 AM
Last modification on : Friday, October 15, 2021 - 1:39:28 PM

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Indira Fabre, Niklas von Wolff, Gaëtan Le Duc, Emmanuel Ferrer Flegeau, Christian Bruneau, et al.. Autocatalytic intermolecular versus intramolecular deprotonation in C-H bond activation of functionalized arenes by ruthenium(II) or palladium(II) complexes.. Chemistry - A European Journal, Wiley-VCH Verlag, 2013, 19 (23), pp.7595-604. ⟨10.1002/chem.201203813⟩. ⟨hal-00879895⟩

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