TY - JOUR
T1 - Implementation of IPPP-CLOPPA-INDO/S method for the study of indirect nuclear spin coupling constants. Its application to molecules containing tin nuclei.
AU - Botek, Edith
AU - Aucar, Gustavo Adolfo
AU - Cory, Marshall G.
AU - Zerner, Michael Charles
PY - 2000
Y1 - 2000
N2 - The inner projection of the polarization propagator, using contributions from localized orbitals, IPPP–CLOPPA, and using the intermediate neglect of the differential overlap model parameterized for spectroscopy, INDO/S, was implemented and used to calculate indirect nuclear spin coupling constants. The resulting model was tested on a group of small- and medium-size model compounds by comparing its performance with that of other semi-empirical methods and experiments where available. It is shown that in general the INDO/S approximation with the use of SN2(0) and 〈rN−3〉 atomic parameters taken from the INDO and AM1 approaches is the most suitable scheme to describe coupling constants. The introduction of atomic parameters for SN2(0) and 〈rN−3〉 in the case of heavy nuclei like Sn, is a critical step. The correction of the bonding beta parameter for this nucleus was also necessary within the INDO/S approximation to improve the accuracy and to better account for indirect relativistic effects. The application of this parameterization was accomplished in a series of tetrastannacyclohexanes and different pathways for coupling transmission were analyzed.
AB - The inner projection of the polarization propagator, using contributions from localized orbitals, IPPP–CLOPPA, and using the intermediate neglect of the differential overlap model parameterized for spectroscopy, INDO/S, was implemented and used to calculate indirect nuclear spin coupling constants. The resulting model was tested on a group of small- and medium-size model compounds by comparing its performance with that of other semi-empirical methods and experiments where available. It is shown that in general the INDO/S approximation with the use of SN2(0) and 〈rN−3〉 atomic parameters taken from the INDO and AM1 approaches is the most suitable scheme to describe coupling constants. The introduction of atomic parameters for SN2(0) and 〈rN−3〉 in the case of heavy nuclei like Sn, is a critical step. The correction of the bonding beta parameter for this nucleus was also necessary within the INDO/S approximation to improve the accuracy and to better account for indirect relativistic effects. The application of this parameterization was accomplished in a series of tetrastannacyclohexanes and different pathways for coupling transmission were analyzed.
U2 - 10.1016/S0022-328X(99)00636-1
DO - 10.1016/S0022-328X(99)00636-1
M3 - Article
SN - 0022-328X
VL - 598
SP - 193
EP - 201
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -