Hydrolysis of element (White) phosphorus under the action of heterometallic cubane-type cluster {mo<inf>3</inf>pds<inf>4</inf>}

Abstract

Reaction of heterometallic cubane-type cluster complexes—[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6, where dba—dibenzylideneacetone, dbbpy—4,4′-di-tert-butyl-2,2′-bipyridine, tu—thiourea, acac—acetylacetonate, py—pyridine, with white phosphorus (P4 ) in the presence of water leads to the formation of phosphorous acid H3PO3 as the major product. The crucial role of the Pd atom in the cluster core {Mo3PdS4 } has been established in the hydrolytic activation of P4 molecule. The main intermediate of the process, the cluster complex [Mo3 {PdP(OH)3 }S4Cl3 (dbbpy)3 ]+ with coordinated P(OH)3 molecule and phosphine PH3, have been detected by31P NMR spectroscopy in the reaction mixture.