Real Catalyst Species Investigation Of Negishi-type Oxidative Coupling Reactions And Mechanism Study Of Peroxide Activity Catalyzed By Copper

This paper is carried out on the basis of kinetic investigation of oxidative coupling reactions, which are studied by using operando React IR instrument. We study the process of reductive elimination which have been proved to be the rate determining step. Although DFT calculations illustrate that Pd catalyzed reaction should be faster than that of Ni at this condition, the kinetic experiments indicate the reaction rate of Pd and Ni is dependent on the concentration of the catalyst precursor. The Pd catalyzed reaction is fester than that of Ni only when the precursor concentration is as bw as 1×10-7 M.By using XAFS and UV-vis instruments, C1-, Br, I- have been proved to be able promote the decay of Pd(dba)2 to form NPs. Kinetic investigations of the decay have been done. DFT results show the mechanism of the Pd NPs formation.Complexes which are formed from Pd(0) and ArZn have been observed by using UV-vis instrument. XAFS results also show that ArZn would decrease the energy of Pd(0)'s pre-edge. Kinetic investigations show that ArZn would take part in the process of oxidative addition.By using operando React IR and XAFS instruments. The process of peroxide compound decomposition catalyzed by copper have been investigated. Anions of copper salts would take part in the redox process as an electron delivery and hydrogen acceptor.