resumo
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.
palavras-chave
ORGANOMETALLIC COMPLEX; CATALYZED HYDROLYSIS; OLEFIN EPOXIDATION; PHOSPHATASE; MOLYBDENUM; CLEAVAGE; N,N-DIMETHYLFORMAMIDE; POLYOXOMOLYBDATES; PYROPHOSPHATE; REACTIVITY
categoria
Chemistry
autores
Tome, CM; Oliveira, MC; Pillinger, M; Goncalves, IS; Abrantes, M
nossos autores
Isabel Maria de Sousa Gonçalves
Professor associado
Martyn Pillinger
Investigador PrincipalProjectos
agradecimentos
We are grateful to the Fundacao para a Ciencia e a Tecnologia (project no. PTDC/EQU-EQU/121677/2010), QREN, FEDER, COMPETE, and the European Union for funding. The Associate Laboratory CICECO (Pest-C/CTM/LA0011/2011) is acknowledged for continued support, including grant no. BI/UI89/6110/2012 to C. M. T. Authors thank the project PEst-OE/QUI/UI0100/2011, the Portuguese NMR Network (IST-UTL Center) for providing access to the NMR facilities and the Portuguese MS Network (IST Node) for the ESI measurements (REDE/1502/REM/2005).