Indirect relativistic bridge and substituent effects from the "heavy' environment on the one-bond and two-bond 13C1H 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 (CH)-C-13-H-1 spin-spin coupling constants are observed, and spin-orbit parts of these two effects were interpreted in terms of the third-order Rayleigh-Schrodinger 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. Copyright (c) 2015 John Wiley & Sons, Ltd.