Distinguishing "Through-Space" from "Through-Bonds" Contribution in Indirect Nuclear Spin-Spin Coupling: General Approaches Applied to Complex JPP and JPSe Scalar Couplings.

We present herein two complementary theoretical approaches for analyzing the transmission pathways of indirect nuclear spin-spin couplings in high-resolution nuclear magnetic resonance. This phenomenon is notably conceptually poorly understood in complex experimental situations in which both nonbonded ["through-space" (TS)] and more "classical" bonding ("through-bond") spin-spin coupling pathways are potentially involved. The computational approaches we propose allow the visualization and discussion of individual transmission pathways and estimation of their relative weight from numerical contributions to the spin-spin coupling constant J-value. The first approach is based on the analysis of contributions limited to occupied molecular orbitals [focused on occupied molecular orbitals (FOMO)]. The second approach encompasses the consideration of both occupied and vacant orbitals [global molecular orbital contributions (GMOC)], and, besides the contributions from individual pathways, also considers their cross contributions. Both approaches are applicable to large systems with complex interactions of nuclear magnetic moments. Herein, we have first applied the FOMO and GMOC computational approaches to simple diphosphine models and then extended the analysis to JPP and JPSe experimentally measured in a constrained selenated (diphosphino)naphthalene compound. The new computational tools contributed evidence for the importance of the single lone pair not only from phosphorus but also from selenium in TS spin-spin transmission. It evidenced and modeled for the first time the existence of spin-spin transmission pathways mixing classical covalent bonding parts with a lone pair overlap of proximate heteroatoms (P and Se).