Ruthenium mediated halogenation of white phosphorus: synthesis and reactivity of the unprecedented PCl moiety.

The transition metal mediated functionalization of P4 is an approach to develop a more sustainable production of organophosphorus compounds. In this paper a ruthenium complex is presented, in which the P4 unit can be selectively converted into new P4R2 molecules in a two-step synthesis. The unsaturated 16 electron species [RuX(Cp*)(PCy3)] (Cp* = C5Me5, X = Cl, Br) reacts with a half equivalent of P4 affording a bimetallic complex bearing a planar P4X2 moiety as a ligand. The latter eliminates chloride anions under reduction with magnesium. In this process the butadiene-like P4Cl2 ligand is converted into two weakly bound P2 units which bridge the ruthenium centers. In the presence of n-BuLi, the P4Cl2 unit can be selectively alkylated, yielding the planar organophosphorus ligand P4nBu2. A detailed analysis of the electronic properties and solid state structures of the compounds combined with DFT calculations and AIM analyses demonstrate that the P4 unit in all complexes acts as an electronically highly flexible, non-innocent ligand.