Indirect relativistic bridge and substituent effects from the 'heavy' environment on the one-bond and two-bond (13)C-(1)H spin-spin coupling constants.
Indirect relativistic bridge effect (IRBE) and indirect relativistic substituent effect (IRSE) induced by the 'heavy' environment of the IV-th, V-th and VI-th main group elements on the one-bond and geminal (13)C-(1)H spin-spin coupling constants are observed, and spin-orbit parts of these two effects were interpreted in terms of the third-order Rayleigh-Schrödinger perturbation theory. Both effects, IRBE and IRSE, rapidly increase with the total atomic charge of the substituents at the coupled carbon. The accumulation of IRSE for geminal coupling constants is not linear with respect to the number of substituents in contrast to the one-bond couplings where IRSE is an essentially additive quantity.
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia.
Irina L
IL
Rusakova
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia.
Yury Yu
YY
Rusakov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia.
Leonid B
LB
Krivdin
D002247:Carbon Isotopes / Q000737:chemistry*; D003198:Computer Simulation; D006859:Hydrogen / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical
D002247:Carbon Isotopes; D006859:Hydrogen
NMR; four-component DFT; indirect relativistic effects; spin-spin coupling constant