Stereoelectronic Contributions to 1H-1H Coupling Constants 英文参考文献.docVIP

539 Molecules 2000, 5 Stereoelectronic Contributions to 1H-1H Coupling Constants E. M. Sproviero and Burton G. Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, UBA. Pabellón II, 3°P. Ciudad Universitaria. (1428). Buenos Aires, Argentina E-mail: esprov@qo.fcen.uba.ar Abstract: The effect of stereoelectronic interactions on coupling constants is shown. The analysis is done with a new approach in which a selected interaction is deleted and the effect over the couplings is analyzed. 1H-1H magnetic couplings three and four bonds apart in hy- drocarbons are shown. Introduction Coupling constants have been widely used to carry out conformational analysis in molecules. In these studies the relationship between structural parameters (dihedral angles) and experimental data (magnetic coupling constants) are provided. For this reason it is interesting to analyze the in- tramolecular interactions that produce Karplus-like curves. Results and Discussion The methodology presented here implies, as a first step, a Natural Bond Order [1] (NBO) localiza- tion, followed by the deletion of selected Fock matrix elements (written in the NBO basis) representa- tive of the interaction between selected orbitals. The next step is to recalculate the density matrix in the AO basis using the modified Fock matrix and then calculate the electronic polarization propagator [2]. With this propagator it is possible to determine several second order properties, like magnetic cou- plings, which are of interest in this work. The magnitude calculated in this way is then compared with the magnitude obtained without deletions and so it is possible to evaluate the effect of the interactions corresponding to the deletions considered. The computations were done with Gaussian 98 (geometry optimizations and NBO analysis) and SYSMO (magnetic properties). Using the present formalism we analyzed coupling constant