- Novel heterometallic palladium-silver complex
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The reaction between Pd3(OOCMe)6 and Ag 2(OOCMe)2 afforded the first palladium-silver heterometallic acetate-bridged complex PdII[(μ-OOCMe) 2AgI(HOOCMe)2]2 (1). The molecular geometry and electronic structure of 1 were studied by single-crystal XRD and quantum-chemical DFT calculations. Thermal transformations of 1 in vacuo and under Ar, H2 produced PdAg alloy nanoparticles characterized with powder XRD and EXAFS.
- Kozitsyna, Natalia Yu.,Nefedov, Sergei E.,Klyagina, Alla P.,Markov, Alexander A.,Dobrokhotova, Zhanna V.,Velikodny, Yuri A.,Kochubey, Dmitry I.,Zyubina, Tatiana S.,Gekhman, Alexander E.,Vargaftik, Michael N.,Moiseev, Ilya I.
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- Mechanistic Insights on Pd/Cu-Catalyzed Dehydrogenative Coupling of Dimethyl Phthalate
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Despite its industrial importance, very limited mechanistic information on the dehydrogenative coupling of dimethyl phthalate has been reported. Herein we report the detailed mechanism for dehydrogenative coupling of dimethyl phthalate catalyzed by [Pd(OAc)2]/[Cu(OAc)2]/1,10-phenanthroline·H2O (phen·H2O). The solution-phase analysis of the catalytic system by XANES shows the active species to be Pd(II), and EXAFS supports the formation of an (acetato)(dimethyl phthalyl)(phen)palladium(II) complex from [Pd(OAc)2]. A formation pathway of tetramethyl 3,3′,4,4′-biphenyltetracarboxylate via disproportionation of independently prepared [Pd(OAc){C6H3(CO2Me)2-3,4}(phen)] is observed with regeneration of [Pd(OAc)2(phen)].
- Hirano, Masafumi,Sano, Kosuke,Kanazawa, Yuki,Komine, Nobuyuki,Maeno, Zen,Mitsudome, Takato,Takaya, Hikaru
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p. 5827 - 5841
(2018/05/29)
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