The Dewar-Chatt-Duncanson (DCD) model provides a successful theoretical framework to describe the nature of the chemical bond in transition-metal compounds and is especially useful in structural chemistry and catalysis. However, how to actually measure its constituents (substrate- to-metal donation and metal-to-substrate back-donation) is yet uncertain. Recently, we demonstrated that the DCD components can be neatly disentangled and the pi back-donation component put in strict correlation with some experimental observables. In the present work we make a further crucial step forward, showing that, in a large set of charged and neutral N-heterocyclic carbene complexes of gold(I), a specific component of the NMR chemical shift tensor of the carbenic carbon provides a selective measure of the sigma donation. This work opens the possibility of 1) to characterize unambiguously the electronic structure of a metal fragment (LAu(In+/0 in this case) by actually measuring its sigma-withdrawing ability, 2) to quickly establish a comparative trend for the ligand trans effect, and 3) to achieve a more rigorous control of the ligand electronic effect, which is a key aspect for the design of new catalysts and metal complexes.
- bond theory
- N-heterocyclic carbenes
- NMR spectroscopy
- DENSITY-FUNCTIONAL THEORY
- ELECTROCHEMICAL PARAMETRIZATION