Heterolytic carbon–iodine bond cleavage by a palladium(i) metalloradical

Abstract

The well-defined Pd(I) metalloradical [Pd(PtBu3)2]+ reacts with aryl and alkyl ioidies at room temperature, yielding [Pd(PtBu3)(μ-I)]2 and phosphonium salts. Pd(II) aryl/alkyl derivates, reflecting net radical oxidative addition of the substrate...

Reversible Single-Electron-Transfer to Oxygen in a Stable N-Heterocyclic Carbene Palladium(I) Metalloradical

“…The weaker coordination of acetone to palladium­(II) makes it less suitable for preventing reduction to palladium­(I). Finally, the formation of the superoxido complex 4 in the noncoordinating solvent 1,2-difluorobenzene indicates that the three-coordinate structure shown in Scheme is stable, at least at low temperatures. ,,− …”

“…A new breakthrough came in 2016, when the Chaplin and Ozerov groups characterized independently the stable palladium­(I) two-coordinate complex [Pd­(P t Bu 3 ) 2 ] + together with its acetonitrile three-coordinate adduct [Pd­(P t Bu 3 ) 2 (NCMe)] + . , More recently, Deng et al and Mirica et al reported tricoordinate amido and tetracoordinate dithiapyridinophane palladium­(I) complexes, respectively. Beyond these synthetic advances, studies on the reactivity of these stable Pd­(I) radicals are still very scarce − despite their importance for a better understanding of palladium-catalyzed radical reactions.…”