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Quantum semiempirical study on the reactivity of silylated diamines in the synthesis of aromatic polyamides
Author(s) -
Lozano Angel E.,
de Abajo Javier,
De la Campa José G.
Publication year - 1998
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/(sici)1521-3919(19980101)7:1<41::aid-mats41>3.0.co;2-g
Subject(s) - silylation , reactivity (psychology) , chemistry , ab initio , molecular orbital , amine gas treating , computational chemistry , density functional theory , medicinal chemistry , polymer chemistry , organic chemistry , photochemistry , molecule , catalysis , medicine , alternative medicine , pathology
The reasons for the reactivity increase toward acyl chlorides caused in aromatic amines by silylation are studied by quantum semiempirical and ab initio methods. Silylated amino groups adopt an sp 2 planar geometry, in contrast to that observed in the unsilylated series, where a partially pyramidal structure intermediate between sp 3 and sp 2 geometry was obtained. Silylation also causes a strong increase of electronic density on the amine nitrogen and an increase of the Highest Occupied Molecular Orbital (HOMO) energy, both effects favoring the higher reactivity of these silylated amines. In addition to that, silylation produces a decrease of the activation energy in the reaction with an acyl chloride, relative to the unsilylated amines, thus increasing reaction rate.