Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo(3)PdS(4)}

Reaction of heterometallic cubane-type cluster complexes—[Mo(3){Pd(dba)}S(4)Cl(3)(dbbpy)(3)]PF(6), [Mo(3){Pd(tu)}S(4)Cl(3)(dbbpy)(3)]Cl and [Mo(3){Pd(dba)}S(4)(acac)(3)(py)(3)]PF(6), where dba—dibenzylideneacetone, dbbpy—4,4′-di-tert-butyl-2,2′-bipyridine, tu—thiourea, acac—acetylacetonate, py—pyridine, with white phosphorus (P(4)) in the presence of water leads to the formation of phosphorous acid H(3)PO(3) as the major product. The crucial role of the Pd atom in the cluster core {Mo(3)PdS(4)} has been established in the hydrolytic activation of P(4) molecule. The main intermediate of the process, the cluster complex [Mo(3){PdP(OH)(3)}S(4)Cl(3)(dbbpy)(3)](+) with coordinated P(OH)(3) molecule and phosphine PH(3), have been detected by (31)P NMR spectroscopy in the reaction mixture.