Density functional theory analysis of dimethylphosphate hydrolysis: effect of solvation and nucleophile variation |
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| Affiliation: | 1. Department of Chemistry, Recep Tayyip Erdoğan (RTE) University, 53100 Rize, Turkey;2. Ondokuz Mayıs University, Education Faculty, Computer Education and Instructional Education Department, 55200 Atakum, Samsun, Turkey;3. University of Vigo, Chemistry Faculty, Inorganic Chemistry Department, Campus Universitario-Lagoas Marcosende, E-36310 Vigo, Spain;1. Department of Chemistry, The University of Burdwan, Burdwan 713 104, India;2. Department of Chemistry, Chung Yuan Christian University, Chung Li 32023, Taiwan, ROC;3. Institut de Chimie Moléculaire et des Matériaux d’Orsay, Université Paris Sud, Batiment 420, F-91405 Orsay, France;1. Departamento de Química Inorgánica/Facultade de Química, Instituto de Investigación Biomédica (IBI), Universidade de Vigo, E-36310 Vigo, Galicia, Spain;2. BCMaterials & Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apartado 644, 48080 Bilbao, Spain;1. IMRCP, CNRS UMR 5623, University of Toulouse, 118, Route de Narbonne, 31062 Toulouse, France;2. The Department of Chemistry, Taras Shevchenko National University of Kyiv, 12, Lva Tolstogo Street, 01033, Kyiv, Ukraine;3. ICT, FR CNRS 2599, University of Toulouse, 118, Route de Narbonne, 31062 Toulouse, France |
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| Abstract: | We model the hydrolytic cleavage of dimethylphosphate by hydroxide ion and water in the gas phase and in implicit water using density functional theory. In all cases the rate-determining step is the nucleophilic attack. The barrier for this nucleophilic attack in vacuum is much larger for the hydroxide than for the neutral nucleophile. However, in water the barriers are similar. The rate-determining step in the attack by the neutral nucleophile involves the concerted transfer of a proton from the water molecule to the phosphate ion and the formation of the P–O bond. |
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