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Title: | Use of MoO2Cl2(DMF)(2) as a precursor for molybdate promoted hydrolysis of phosphoester bonds |
Author: | Tome, Catia M. Conceicao Oliveira, M. Pillinger, Martyn Goncalves, Isabel S. Abrantes, Marta |
Keywords: | ORGANOMETALLIC COMPLEX CATALYZED HYDROLYSIS OLEFIN EPOXIDATION PHOSPHATASE MOLYBDENUM CLEAVAGE N,N-DIMETHYLFORMAMIDE POLYOXOMOLYBDATES PYROPHOSPHATE REACTIVITY |
Issue Date: | 2013 |
Publisher: | ROYAL SOC CHEMISTRY |
Abstract: | Phosphoester bond cleavage of para-nitrophenylphosphate (pNPP), a commonly used model substrate, is accelerated by using the complex MoO2Cl2(DMF)(2) (1) (DMF = dimethylformamide) as a hydrolysis promoting agent, even when catalytic amounts of 1 (10 mol% relative to pNPP) are used. The reactions were performed under mild conditions (37-75 degrees C) and followed by H-1 NMR spectroscopy. For assays performed with high amounts of 1 (1000 mol% relative to pNPP), a white solid (2) precipitates during the initial stages of the reaction, which subsequently dissolves, leading eventually to the precipitation of a less soluble yellow solid (3). Taken together, the characterization data for 2 (FT-IR spectroscopy, elemental analysis, H-1 and C-13 NMR, and electrospray ionization mass spectrometry) indicate that it is a polymeric material with the formula Mo2O6(DMF)(n) and a structure comprising infinite isopolyoxomolybdate chains built up from edge-shared {MoO6} octahedra. Compound 3 was identified as the Keggin-type phosphomolybdate [(CH3)(2)NH2](3)PMo12O40. The formation of 3 is explained by the reaction of inorganic phosphate ions with isopolymolybdate species derived from 2, with dimethylammonium ions arising from the degradation of DMF. Both 2 and 3 are active for phosphoester bond hydrolysis with conversion profiles comparable to the ones obtained with the precursor 1. |
Peer review: | yes |
URI: | http://hdl.handle.net/10773/20672 |
DOI: | 10.1039/c2dt32734a |
ISSN: | 1477-9226 |
Publisher Version: | 10.1039/c2dt32734a |
Appears in Collections: | CICECO - Artigos |
Files in This Item:
File | Description | Size | Format | |
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Use of MoO2Cl2(DMF)2 as a precursor for molybdate promoted hydrolysis of phosphoester bonds_10.1039c2dt32734a.pdf | 423.45 kB | Adobe PDF |
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