Use of Organomolybdenum Compounds for Promoted Hydrolysis of Phosphoester Bonds in Aqueous Media

Abstract

The dissolution of the indenyl (Ind) complex [{(eta(5)-Ind)Mo(CO)(2)(mu-Cl)}(2)] (1) in N,N'-dimethylformamide (DMF) gives the ring-slipped complex [(eta(3)-Ind)Mo(CO)(2)Cl(DMF)(2)] (2). The aerial oxidation of 2 leads to the formation of the dinuclear oxomolybdenum(V) chloride [Mo2O2(DMF)(4)(mu-O)(2)Cl-2] (3). The structures of 2 and 3 DMF have been determined by single-crystal X-ray diffraction. Compounds 1 and 3 were examined as promoters of phosphoester bond hydrolysis in para-nitrophenylphosphate (pNPP), which was used as a model substrate. The reactions were performed in aqueous solution at 55 degrees C and followed by H-1 NMR spectroscopy. For assays performed with 30-100 mol-% of 1 or 3 relative to pNPP, both compounds promote the production of para-nitrophenol (pNPh) from pNPP. Compound 3 is especially active in promoting the hydrolytic cleavage of the phosphoester bond (t(1/2) < 80 min).