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The Hirao reaction, an important tool for the establishment of a P-C bond, was developed further by finding that the reaction of >P(O)H species, such as dialkyl phosphites, alkyl phenyl-H-phosphinates and diarylphosphine oxides with bromoarenes may be carried out in the presence of P-ligand-free NiCl2 as the catalyst. The scope and limitations of this “greener” approach was studied in detail.