Copper(i) activation of C–X bonds: bimolecularvs.unimolecular reaction mechanism

Abstract

Experimental kinetic studies and DFT calculations show that the oxidative addition of aryl halides (Ar–X) to complexes [Cu(NHC)R] follow different paths depending on the nature of X. For X =...

Application of statistical learning and mechanistic modelling towards mapping the substrate electronic space in a Cu-catalyzed Suzuki–Miyaura coupling

“…Dinuclear oxidative addition transition states were not taken into consideration because of the low concentration of the initial catalytic species. 76 After the oxidative addition, intermediate I 6 should be formed; however, all the attempts to optimize this formally Cu( iii ) species with the regular computational settings, including different trigonal bipyramidal and square pyramidal complexes, have led to the formation of the final product (PhC 6 F 5 ), indicating that the reductive elimination process seems to be barrierless. This behavior has been reported before by Bolm in a computational study of a copper-catalyzed Sonogashira coupling.…”

Molecular Weight Determination of Relevant Organometallic Catalysts in Solution by DOSY-NMR to Monitor Reactivity

“…The ICC method could clarify the aggregational behavior of various compounds under investigation, for example, cyclopentyllithium and cyclopentyllithium thf complex. − Still, the ICC method reveals a few drawbacks, which could be overcome by the implementation of the external calibration curves (ECCs) in our group. − The underlying principle is the use of an external fixed diffusion (log( D ref,fix )) coefficient for a certain standard depending on the solvent, e.g., adamantane in toluene, to which the experimental diffusion coefficient of the sample (log( D x )) and the diffusion coefficient of an added standard (log( D ref )) are related (eq ). log ( D x , norm ) 0.25em = 0.25em log ( D x ) 0.25em + 0.25em ( log false( D ref , fix false) − log false( D ref false) ) The ECC method has shown its potential, for example, in the determination of the aggregation behavior in solution − or the identification of the oligomeric equilibrium of LDA in toluene . Recently, progress has been made to apply the ECC method to investigate natural products involved in various hydrogen bonds .…”