title: Theoretical studies on the mechanism of C-P bond cleavage of a model alpha-aminophosphonate in acidic condition.
abstract: Various reaction paths of the P-C bond cleavage of alpha-aminophosphonates in acidic media, resulting in the derivatives of phosphonic acid, has been investigated using density functional level of theories in the gas phase as well as in aqueous medium. Dimethyl (alpha-anilinobenzyl)phosphonate has been used as the model molecule and our investigation confirms a three steps process including protonation, P-C bond cleavage, and the transformation of the products from the final transition state (imine cation and H-phosphonate) through hydrolysis. The most favorable reaction path starts from the amino group protonation, followed by a proton transfer through N-H...O(P) hydrogen bond, and the P-C bond cleavage from the resulting protonated structure. Explicit inclusion of water molecules indicated that two waters are needed for the P-C bond cleavage, and the calculated mechanistic paths in this hydrated model are similar to those of the aqueous solvation model.
authors.affiliation: Computational Center for Molecular Structure and Interactions, Jackson State University, Jackson, Mississippi 39217, USA.
authors.forename: Marek
authors.initials: M
authors.lastname: Doskocz
authors.forename: Szczepan
authors.initials: S
authors.lastname: Roszak
authors.forename: D
authors.initials: D
authors.lastname: Majumdar
authors.forename: Jacek
authors.initials: J
authors.lastname: Doskocz
authors.forename: Roman
authors.initials: R
authors.lastname: Gancarz
authors.forename: Jerzy
authors.initials: J
authors.lastname: Leszczynski
mesh_terms: D000143:Acids / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D004735:Energy Transfer; D006860:Hydrogen Bonding; D008956:Models, Chemical; D015394:Molecular Structure; D063065:Organophosphonates / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D011522:Protons; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D000143:Acids; D000588:Amines; D063065:Organophosphonates; D011522:Protons; D014867:Water; D010758:Phosphorus; D002244:Carbon