From Azobenzene Coordination to Aryl−Halide Bond Activation by Platinum

This contribution describes the reactivity of Pt(PEt3)4 with (4-bromo-phenyl)-pyridin-4-yl-diazene. η2-Coordination of Pt(PEt3)2 to the NN moiety is kinetically preferable and followed by an aryl−halide bond activation process. This quantitative transformation proceeds under mild reaction conditions in solution and in the solid state. Mechanistic studies in solution indicate that the metal insertion into the aryl−halide bond is the rate-determining step. The reaction obeys first-order kinetics in the η2-coordination complex with ΔG⧧298K = 24.6 ± 1.6 kcal/mol, ΔH⧧ = 26.5 ± 1.6 kcal/mol, and ΔS⧧ = 6.6 ± 5.0 eu. No effect on the reaction progress and NMR line shape has been observed in the presence of excess PEt3. However, competition experiments with the η2-coordination complex and PhBr reveal that the product ratio can be altered by the presence of PEt3, indicating that the two aryl−halide bond activation processes proceed via different mechanistic pathways. Numerical analysis of a series of competition ex...