Syntheses and Thermolysis of Arylpalladium Hydroxide Complexes: Implications for C(sp2)–OH Bond-Forming Reductive Elimination To Generate Phenol Derivatives

Abstract

The decomposition of arylpalladium hydroxide complexes gave the corresponding phenolic products, which may form through a C(sp2)–OH bond-forming reductive elimination either by treatment of arylpalladium halide complexes with cesium hydroxide or by heating arylpalladium hydroxide complexes. Treatment of a p-nitrophenylpalladium iodide complex possessing a tBuXPhos ligand with cesium hydroxide formed a mixture of p-nitrophenol and 4,4′-di-p-nitrobiphenyl. The reaction of a DtBPP-ligated p-nitrophenylpalladium iodide complex with cesium hydroxide gave a mixture of p-nitrophenylpalladium hydroxide complex, cesium p-nitrophenoxide, and DtBPP-bridged dinuclear Pd(0) complex. Gradual decomposition of p-nitrophenylpalladium hydroxide complex to cesium p-nitorophenoxide and a DtBPP-bridged dinuclear Pd(0) complex suggested that the C(sp2)–OH bond-forming reductive elimination took place. While an isolated p-tolylpalladium hydroxide complex gave no phenolic product upon heating, thermolysis of an isolated trifluoromethyl-substituted arylpalladium hydroxide complex enabled us to observe p-trifluoromethylphenol directly. Although an ester-substituted hydroxide complex did not form free p-methoxycarbonylphenol, its invisibility enabled us to handle the kinetic equation to estimate the rate constant k1 for reductive elimination. Polar solvents such as THF and DMF accelerated the reductive elimination with a large negative entropy of activation. Comparison of these results with those in the literature suggested direct C(sp2)–OH bond-forming reductive elimination with a concerted three-centered pathway. DFT calculations also predicted the hydrogen bond between the hydroxo ligand and the solvent molecule to stabilize the transition state.