Arene C−H Bond Activation and Arene Oxidative Coupling by Cationic Palladium(II) Complexes

Abstract

N,N'-Diaryl-α-diimine-ligated Pd(II) dimethyl complexes (^(tBu)2^(Ar)DAB^(Me))PdMe_2 and {(CF_3)_2^(Ar)DAB^(Me)}PdMe_2 {^(tBu)2^(Ar)DAB^(Me): ArNC═(CH_3)−C(CH_3═NAr, Ar=3,5-di-tert-butylphenyl; (CF_3)_2^(Ar)DAB^(Me):Ar = 3,5-bis(trifluoromethyl)phenyl} undergo protonolysis with HBF_4(aq) in trifluoroethanol (TFE) to form cationic complexes [(α-diimine)Pd(CH_3)(H_2O)][BF_4]. The cations activate benzene C−H bonds at room temperature. Kinetic analyses reveal trends similar to those observed for the analogous platinum complexes:  the C−H activation step is rate-determining (KIE = 4.1 ± 0.5) and is inhibited by H_2O. The kinetic data are consistent with a mechanism in which benzene substitution proceeds by a solvent- (TFE-) assisted associative pathway. Following benzene C−H activation under 1 atm O_2, the products of the reaction are biphenyl and a dimeric μ-hydroxide complex, [(α-diimine)Pd(OH)]_2[BF_4]_2. The Pd(0) formed in the reaction is reoxidized by O_2 to the dimeric μ-hydroxide complex after the oxidative C−C bond formation. The regioselectivity of arene coupling was investigated with toluene and α,α,α-trifluorotoluene as substrates.

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