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

authors	Gomes, AC; Gamelas, CA; Fernandes, JA; Paz, FAA; Nunes, P; Pillinger, M; Goncalves, IS; Romao, CC; Abrantes, M
nationality	International
journal	EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
author keywords	Indenyl ligands; Molybdenum; Coordination modes; Oxido ligands; Phosphoesters; Hydrolysis
keywords	ALPHA-PINENE OXIDE; ORGANOMETALLIC COMPLEX; MICELLAR-SOLUTION; INDENYL ANALOGS; RING SLIPPAGE; MIXED-RING; MOLYBDENUM; DERIVATIVES; CLEAVAGE; CATALYST
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).
publisher	WILEY-V C H VERLAG GMBH
issn	1434-1948
year published	2014
issue	23
beginning page	3681
ending page	3689
digital object identifier (doi)	10.1002/ejic.201402071
web of science category	Chemistry, Inorganic & Nuclear
subject category	Chemistry
unique article identifier	WOS:000340564700008