Abstract
The mechanism of alcoholysis of acylpalladium(II) complexes relevant to the alternating copolymerisation of ethene and carbon monoxide has been investigated theoretically in detail. The solvolysis of acylpalladium(II) complexes is an important step in palladium-catalysed reactions. Based on experimental studies, two mechanisms have been proposed for this process, which consist of a concerted reductive elimination and an insertion mechanism (reductive elimination via a Meisenheimer intermediate). Both mechanisms include deprotonating of an acylpalladium(II) complex and according to our calculations, any mechanism involving this step, has an energy barrier higher than that of the rate-determining step. We propose a new mechanism for the insertion in which proton transfer to Pd is simultaneous with an inner-sphere attack of the alkoxide ligand (OCH3) at the carbon atom of the palladium-bound carbonyl group (new Meisenheimer intermediate). Considering solvent effects, the activation energies of the two mechanisms and other contingent mechanisms were calculated and compared with each other and the experimental results.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
