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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 21, Number 9
BKCSDE 21(9)
September 20, 2000 

Catalytic Effect of MO42- (M=Cr, Mo and W) on Hydrolyses of Carbon and Phosphorus Esters
Byung-Tae Ahn,* Hee-Sun Park, Eun-Ju Lee, lk-Hwan Urn*
Second-order rate constants have been measured spectrophotometrically for the hydrolysis of p-nitrophenyl ac-etate (PNPA) and p-nitrophenyl diphenylphosphinate (PNPDPP) with MO42- (M = Cr, Mo and W) in phos-phate buffer (pH = 8.00) at35.0 ℃. These MO42- species exhibit large catalytic effect in the hydrolysis of PNPA and PNPDPP except WO42- in the reaction with PNPA. The catalytic effect of these MO42- species has been observed to be much more significantin the hydrolysis of PNPDPP than in the hydrolysis of PNPA. Since the smallest CrO42-would be most highly solvated by H2O molecules, CrO42- is expected to exhibit the least catalytic effect, if solvation effect is the most important factor. However, in fact, CrO42- shows the highest cat-alytic effect toward PNPA, indicating that solvation effect is not solely responsible for the catalytic effect. The most basic CrO42- shows the highest catalytic effect, while the least basic WO42- is least reactive toward PNPA, indicating that the basicity of MO4 2- might bean important factor. However, in the hydrolysis of PNPDPP, no correlation is observed between the basicity and catalytic effect, suggesting thatbasicity alone can not be re-sponsible for the catalytic effect shown by the MO42- species. Formation of a chelate is suggested to be respon-sible for the high catalytic effect of MO42- in the hydrolysis reaction of PNPA and PNPDPP. The formation of chelate is considered to be more suitable for the reaction with PNPDPP than with PNPA based on the larger catalytic effect observed in the reaction with PNPDPP than with PNPA.
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