Rapid geometrical equilibrium of palladium(II) complexes with tris[2-(diphenylphosphino)ethyl]phosphine disulfide and diselenide and their catalytic activity for Suzuki coupling reaction

Palladium(II) complexes with a tetradentate pseudo-tripodal ligand having two phosphino groups and two phosphine sulfide or selenide groups, pp₃X₂ (pp₃ = tris[2-(diphenylphosphino)ethyl]phosphine, X = S (1) or Se (2)), were prepared from [PdCl(pp₃)]Cl. Both of these phosphine chalcogenide complexes 1 and 2 showed rapid equilibrium between the five-coordinate [PdCl(pp₃X₂)]Cl with two bound phosphine chalcogenide groups and four-coordinate [PdCl₂(pp₃X₂)] with two dissociated pendant ones in chloroform. The thermodynamic parameters for the reaction, [PdCl(pp₃X₂)]⁺ + Cl^-⇄[PdCl₂(pp₃X₂)], were obtained by low-temperature ³¹P NMR as follows: K²⁹⁸ = 3.7 × 10³ and 5.4 × 10² mol^-1, ΔH^{{ring operator}} = 11.3 ± 0.3 and 13.4 ± 0.4 kJ mol^-1, and ΔS^{{ring operator}} = 106 ± 2 and 97 ± 2 J mol^-1 K^-1 for 1 and 2, respectively. The rate for the geometrical change at 246.7 K for 1 was appreciably faster than that for 2. These thermodynamic and kinetic results indicate that the phosphine selenide Se atoms can stabilize the five-coordinate structure by effective π-back donation from Pd(II) compared with the phosphine sulfide S atoms. Difference in retention of the catalytic activity for Suzuki coupling, 2 > 1 > [PdCl(pp₃ or p₃)]Cl, was explained by difference in the π-accepting ability that stabilizes the catalytically active Pd(0) species. Considering the rapid dissociation-coordination equilibrium of the phosphine chalcogenide groups on Pd(II), it is probable that the oxidative addition and the subsequent transmetallation of the Pd(II) species are hardly blocked by the phosphine chalcogenide groups.