Understanding the Ligand Influence in the Multistep Reaction of Diazoalkanes with Palladium Complexes Leading to Carbene-Aryl Coupling.

ABSTRACT: The reaction of diphosphino aryl complexes [Pd(C₆F₅)(L-L)(NCMe)](BF₄) (L-L = dppe, dppp, dppb) with diazoalkanes N₂CHR (R = -CH=CHPh, Ph) leads to η³-allyl or η³-benzyl palladium derivatives that are the organometallic products resulting from carbene-aryl coupling. The experimental trend shows that the reaction is favored for dppe > dppp > dppb. It involves several consecutive steps, i.e., diazoalkane coordination, nitrogen extrusion to give a Pd-carbene, and migratory insertion, which are experimentally inseparable, but they can be studied with the help of DFT calculations. The bulkiness and bite angle of the ligand exert a large influence in the relative rate of the steps involved in the reaction, and we have found

SUBMITTER: Villalba F 

PROVIDER: S-EPMC11776105 | biostudies-literature | 2025 Jan

REPOSITORIES: biostudies-literature