15638-55-8Relevant academic research and scientific papers
Activation of Benzene Carbon-Hydrogen Bonds by Palladium(II) Acetate-Dialkyl Sulphide Systems
Fuchita, Yoshio,Hiraki, Katsuma,Kamogawa, Yasuko,Suenaga, Miho
, p. 941 - 942 (1987)
Benzene is directly activated by palladium(II) acetate-dialkyl sulphide systems at 70 deg C to afford acetato-bridged diphenyltripalladium(II) complexes , which are regarded as intermediate species in the catalyti
Palladium-catalyzed cross-coupling reactions with fluorinated substrates: Mechanistic insights into the undesired hydrodehalogenation of aryl halides
Orbach, Meital,Choudhury, Joyanta,Lahav, Michal,Zenkina, Olena V.,Diskin-Posner, Yael,Leitus, Gregory,Iron, Mark A.,Van Der Boom, Milko E.
, p. 1271 - 1274 (2012/04/10)
We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of ArF-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.
Activation of Aromatic Carbon-Hydrogen Bonds by Palladium(II) Acetate-Dialkyl Sulfide Systems. Formation and Characterization of Novel Diphenyltripalladium(II) Complexes
Fuchita, Yoshio,Hiraki, Katsuma,Kamogawa, Yasuko,Suenaga, Miho,Tohgoh, Kazutaka,Fujiwara, Yuzo
, p. 1081 - 1085 (2007/10/02)
Palladium(II) acetate reacts wuth benzene in the presence of dialkyl sulfides at 70 deg C to afford novel diphenyltripalladium(II) complexes of 1SR2)PhPd(μ-MeCO2)2Pd(μ-MeCO2)2PdPh(R1SR2)> (1a; R1=But, R2=CH2But; 1b; R1=R2=But: 1c; R1=R2=Pri; 1d; R1=R2=Et) Adducts, tSCH2Bu')2> and i2)2>, prepared by the reactions of palladium(II) acetate and the corresponding dilakyl sulfides in benzene at 5-10 deg C, change to 1a and 1c, respectively, on heating in benzene at 70 deg C.In contrast, reactions of palladium(II) acetate with toluene or thiophene in the presence od diisopropyl sulfide afford no isolable tolyl- or thienyl-palladium species, but coupling products, i.e. bitolyls or bithienyls, are detected by GLC analysis.Treatment of 1b with styrene produces trans-stilbene, whereas 1c reacts with carbon monoxide as well as carbon dioxide to yield benzoic acid.When palladium(II) acetate and t-butyl phenethyl sulfide are heated at 80 deg C in benzene, an adduct tSCH2CH2Ph)2> is formed, in sharp contrast with the case of benzyl t-butyl sulfide, which gives a cyclopalladated complex under the same reaction conditions.
