Photoinduced Homolysis of the Ni-P Bond via Ligand to Metal Charge Transfer for C-P Bond Formation in Nickel Catalysis

Photoinduced homolysis of NiII-carbon and -heter-oatom bonds has been well studied for carbon-heteroatom couplings, but homolysis of the NiII-P bond is still undisclosed. Herein, we describe the homolysis of NiII-P bonds via ligand to metal charge transfer to access active nickel(I) complexes and phosphorus-centered radicals under visible-light irradiation for C-P couplings of diaryl phosphine oxides with aryl bromides. Experimental studies demonstrated that visible light enabled homolysis of the NiII-P bond and the NiI/NiIII self-sustained cycle was involved in C-P bond formation. Furthermore, homolysis of the NiII-P bond can be applied to the hydrophosphination of [1.1.1]propellane in single-nickel photocatalysis.