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The modeling of nucleophilic and electrophilic additions and substitutions using extended Hückel‐based reaction potentials
Author(s) -
Daul Claude,
Goursot Annick,
Morgantini PierreYves,
Weber Jacques
Publication year - 1990
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560380505
Subject(s) - supermolecule , chemistry , computational chemistry , extended hückel method , atomic orbital , polarizability , polarizable continuum model , electrophile , molecular orbital , nucleophile , hamiltonian (control theory) , solvent effects , molecular physics , chemical physics , quantum mechanics , physics , solvent , molecule , organic chemistry , mathematical optimization , mathematics , catalysis , electron
A new formalism has been developed in order to evaluate intermolecular interaction energies for organometallic complexes including electrostatic, polarization, and orbital contributions based on extended Hückel molecular orbital ( EHMO ) theory. The electrostatic interaction is evaluated using (i) a multipolar expansion of EHMO charge density, or (ii) by calculating directly the electrostatic integrals in the basis of atomic orbitals. The polarization effects are evaluated by introducing a perturbation into the Hamiltonian. The orbital interaction is calculated by considering a supermolecule made of the organometallic substrate and a model electrophile or nucleophile. To provide the shortest possible response time on an interactive computer graphics facility, this model should require the minimum amount of computer time, which explains why approximate procedures are used to evaluate the dominant contributions to the interaction energies. Preliminary results show that these interaction energies lead to reaction potentials in good agreement with experiment for a broad series of nucleophilic and electrophilic addition or substitution reactions involving organometallic complexes. In addition, it is shown that the method can easily be extended for the calculation of solvent effects. To this end, developments considering the supermolecule surrounded by a polarizable continuum are in progress.