Definitive Evidence for the Insertion of Terminal Alkynes into ArylS[BOND]Pt Bonds: “o-Halogen Effect” in Stoichiometric and Catalytic Reactions


  • F.Y. thanks the Center of Excellence (21COE) program “Creation of Integrated EcoChemistry” of Osaka University.


original image

An unexpected acceleration of the insertion of terminal alkynes into the S[BOND]Pt bond of complexes 1 was observed when an o-halogen substituent was present in the SAr moiety (see scheme). The reaction rates for G=o-Cl, o-Br, or o-I were much greater than for electron-donating or electron-withdrawing groups. This “o-halogen effect” was also found to be relevant to the Pd-catalyzed addition of (ArS)2 to alkynes.