The first nickel-catalyzed phosphinylation of C–S bonds forming C–P bonds is developed. The reaction can proceed readily with the simple Ni(cod) ₂ at a loading down to 0.1 mol% at the 10 mmol scale. Various aryl sulfur compounds, i.e. sulfides, sulfoxides and sulfones all couple with P(O)–H compounds to produce the corresponding organophosphorus compounds, which provides an efficient new method for the construction of C–P bonds.

Nickel-catalysed P–H/C–CN cross coupling reactions take place efficiently under mild reaction conditions affording the corresponding sp ² C–P bonds. This transformation provides a convenient method for the preparation of both arylphosphines and arylphosphine oxides from the readily available P–H compounds and arylnitriles.

Various valuable phosphinothioates and phosphinates including those with functional groups are readily prepared under mild reaction conditions via chloroform-based Atherton–Todd-type reactions of secondary phosphine oxides with alcohols and thiols, respectively.