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



The dissolution of the indenyl (Ind) complex [{(η5-Ind)Mo(CO)2(μ-Cl)}2] (1) in N,N′-dimethylformamide (DMF) gives the ring-slipped complex [(η3-Ind)Mo(CO)2Cl(DMF)2] (2). The aerial oxidation of 2 leads to the formation of the dinuclear oxomolybdenum(V) chloride [Mo2O2(DMF)4(μ-O)2Cl2] (3). The structures of 2 and 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 °C and followed by 1H 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 (t1/2 < 80 min).