The Analysis of NMR Magnetic Shieldings of Transition Metal (M)-Containing Molecules, M Belonging to Groups IIB, VIB and VIIIB, by Applying the LRESC-Loc Model

We studied the electronic origin of the NMR nuclear magnetic shieldings (σ) of compounds containing the following transition metal atoms: M= Zn, Cd, Hg, Co, Rh, Cr, Mo, W. The electronic mechanisms that underlie the relativistic effects on those shieldings were assessed with the LRESC–Loc model, which permits one to quantify the set of leading relativistic electronic mechanisms responsible for such effects in terms of well-known non-relativistic operators, and also allows for the determination of which molecular orbitals (MOs) are involved in each of those mechanisms. These MOs are such that the chemist’s intuition associated with core, lone-pair (LP), and bonding MOs is satisfied. The LRESC model is a reliable semi-relativistic methodology that has been shown to reproduce, in a semiquantitative manner, the magnetic shieldings and experimental chemical shifts of transition metals in a large set of molecules. Several new features appear in the shieldings analyzed. Trends in the total shieldings within a given family of compounds depend on relativistic effects—the spin-orbit mechanism is one of the most involved—though, within it, one must consider the Fermi contact (FC) and the spin-dipolar (SD) mechanisms. We found that the contributions that are due to partially filled d atomic orbitals (AOs) become too large when the electron correlation is not properly included. This is overcome in our case using density functional theory. A large influence of lone-pairs of π-type on σ(M) is also seen in some of the molecules studied.