Computational exploration of Cu(II)-en chelate-catalyzed hydrolysis of O-isopropyl methylphosphonofluoridate

• Published in: Journal of molecular modeling 2023-07, Vol.29 (7), p.211-211, Article 211
• Main Authors: Khan, Md Abdul Shafeeuulla, Bhanuchander, Nellore, Reddy, Jaggavarapu Satyanarayana, Anna, Venkateswaara Rao, Ganguly, Bishwajit
• Format: Article
• Language: English
• Subjects: Activation energy; Catalysis; Characterization and Evaluation of Materials; Chelates; Chelation; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Configurations; Copper; Copper - chemistry; Copper compounds; Eigenvalues; Eigenvectors; Free energy; Hessian matrices; Hydrolysis; Ligands; Mathematical analysis; Metals - chemistry; Molecular Medicine; Nucleophiles; Optimization; Organophosphorus Compounds - chemistry; Original Paper; Saddle points; Sarin; Solvation; Stability tests; Structural stability; Substrates; Theoretical and Computational Chemistry; Water - chemistry; Wave functions
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-023-05614-4

Context In contrast to un-catalyzed hydrolysis of organophosphorus (OP) compounds, metal ions or/and their complexes with chelating ligands show catalytic effects in several ways depending upon the nature of the metal, ligand, substrate, and medium. It is known that Cu(II)-en chelate containing copper complexes accelerate the hydrolysis of OP compounds. However, the mechanism for this rate enhancement in the Cu(II)-en chelate catalytic hydrolysis reaction of sarin remains unexplored. We have examined possible mechanisms involving a Cu(II)-en with hydroxide nucleophile for the reaction pathway of the hydrolysis of O -isopropyl methylphosphonofluoridate (sarin) computationally. The density functional (B3LYP) employed in this study has reproduced the experimental Gibb’s free energy of activation value 15.5 kcal/mol for alkaline hydrolysis of sarin. Earlier proposal of push–pull mechanism for metal ion chelate-catalyzed hydrolysis of OP compounds has been found to be unfavorable in the present study. The role of water molecules in catalyzing the hydrolysis of sarin with Cu(II)-en chelate is crucial. The catalytic process involving Cu(II)-en chelate with one water molecule is the more plausible pathway to achieve the hydrolysis of sarin with Cu(II)-en chelate complexes. Methods The most popular B3LYP method was used for optimization of given geometries. Except LANL2DZ for Cu atom, all the atoms are described using the 6–31 + G(d) basis set. The stability test has been performed for the wave functions as we are dealing with the open-shell molecules in order to ensure stable electronic configuration form, and the stable wavefunction is used as the initial configuration for the subsequent optimization. Harmonic frequency calculations and thermodynamic corrections were performed at the same level of theory. PCM method has been used for solvation effects. In order to ensure that each saddle point is linked to a minimum, IRC calculations were performed in forward and reverse directions to ensure the eigenvectors associated with the unique negative eigenvalues of the Hessian matrix. All energies discussed are solvated Gibbs free energies corrected to 298.15 K for the relative stability of the chemical structure. All calculations were performed using the Gaussian 09 code.