After a general introduction to the current state of potential energy functions for delineating the steric requirements of exchange reactions, we proceed to a qualitative, Walsh-diagram-based orbital analysis of the preferred geometry approach to the barrier to such reactions. Extended Huckel calculations, perturbation theory, and a frontier orbital perspective are used to analyze the X + H-2 (collinear, due to the controlling role of the singly occupied highest molecular orbital), X + HX, X + HY (also collinear), H + X2 (bent, due to interaction with a relatively low lying unfilled orbital), H + XY (a preference for direction of attack depending on relative electronegativities), M + X2, M + XY, M + HX (collinear approach slightly preferred), X + XY, and triplet O atom reactions.

MOLECULAR-ORBITAL ANALYSIS OF THE ORIENTATION-DEPENDENT BARRIER TO DIRECT EXCHANGE-REACTIONS / D.M. PROSERPIO, R. HOFFMANN, R. LEVINE. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 113:9(1991), pp. 3217-3225.

MOLECULAR-ORBITAL ANALYSIS OF THE ORIENTATION-DEPENDENT BARRIER TO DIRECT EXCHANGE-REACTIONS

D.M. PROSERPIO
Primo
;
1991

Abstract

After a general introduction to the current state of potential energy functions for delineating the steric requirements of exchange reactions, we proceed to a qualitative, Walsh-diagram-based orbital analysis of the preferred geometry approach to the barrier to such reactions. Extended Huckel calculations, perturbation theory, and a frontier orbital perspective are used to analyze the X + H-2 (collinear, due to the controlling role of the singly occupied highest molecular orbital), X + HX, X + HY (also collinear), H + X2 (bent, due to interaction with a relatively low lying unfilled orbital), H + XY (a preference for direction of attack depending on relative electronegativities), M + X2, M + XY, M + HX (collinear approach slightly preferred), X + XY, and triplet O atom reactions.
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/178207
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