Abstract
DFT/B3LYP calculations have been carried out to study intramolecular 1,n aryl-to-aryl palladium shifts (n = 3−6) in polyaryl systems. Such rearrangements, which are associated with a concomitant shift of a hydrogen atom, have been found experimentally to be a pivotal step of several organic transformations mediated by palladium complexes. From the calculations of the various transition states and intermediates involved in the process, the intimate mechanism for the 1,3 shift is shown to correspond to a Pd(IV) pathway, whereas a Pd(II) pathway is favored in the case of 1,5 and 1,6 migrations. In the case of 1,4 migrations, both mechanisms become competitive. The Pd(IV) pathway can involve either a true Pd(IV) intermediate (oxidative addition mechanism) or a Pd(IV) transition state (oxidative hydrogen migration mechanism). The energy barrier is very high for the 1,3 palladium shift, making this process very unlikely, in contrast to the other ones, which have enthalpy barriers ranging between 17.8 and 27.5 k...
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.
