Journal of Physical Chemistry A, Vol.117, No.20, 4304-4315, 2013
On the Chemical Shifts of Agostic Protons
Agostic hydrogen atoms in planar d(8) transition metal complexes display a remarkable wide range of chemical shifts from +5 to -10 ppm in the proton NMR spectra. It is therefore surprising that a simple recipe can be elaborated to predict the influence of the local electronic structure of the metal atom on the shielding of the coordinating protons: In cases where the agostic hydrogen atom is pointing to a local Lewis acidic center at the metal the H-1 NMR signal is shifted upfield relative to the scenario where the proton is opposing a local charge concentration at the metal. To trace the physical origin of this empirical relationship, a systematic study has been performed to understand how the (i) topology of the electron density and (ii) orientation of the magnetic field vector, B-0, control the paratropic or diatropic characteristics of the induced current density at the metal atom and thus the shielding or deshielding of the agostic protons.