Density functional study of the interaction of 3-(ω-bromoacetyl)coumarin with phosphites.

Autor: Nathaniel, Rachel, Mineva, Tzonka, Nikolova, Rositca, Bojilova, Anka
Předmět:
Zdroj: International Journal of Quantum Chemistry; 2006, Vol. 106 Issue 6, p1357-1366, 10p, 2 Diagrams, 8 Charts
Abstrakt: Structural parameters and vibrational frequencies of 3-(ω-bromoacetyl)coumarin, trialkyl and triphenyl phosphites, β-oxophosphonates, and vinyl phosphates computed at the density functional level of theory (BP86 and B3LYP) are presented. In addition, atomic reactivity indices (fukui functions and total hardness) were obtained to gain a better understanding of the regioselectivity observed in the reaction of 3-(ω-bromoacetyl)coumarin with trisubstituted phosphites. An algorithm based on the atomically resolved hardness tensor was employed. Because the atomic fukui function values of the concurrent reactive centers were found to be alike, no conclusion on that basis can be drawn. Relations between total hardnesses of the six products (β-oxophosphonates and vinyl phosphates) were found to follow the relative energy stability trend in agreement with the maximum hardness principle. The lower-energy stability of the vinyl phosphates was attributed mostly to the softening/delocalization of the phosphorus atoms. Phosphorous atom in diphenyl-1-(2-oxo-2H-chromen-3-yl)-2-vinylphosphate was found to be the softest one among the other vinyl phosphates. Unlikely, strong localization/hardening of phosphorus atom in diphenyl-2-(2-oxo-2H-chromen-3-yl)-2-oxoethylphosphonate was obtained. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje