Furthermore, the experimental chemical shifts represent an average over large number of molecules that move over a relativity long time scale, as opposed to the chemical shift from single stationary molecule optimized in the gas phase as computed here; the time scales required for examining these equilibria are out of reach for the ab initio molecular dynamics that would be required to model the M-THF dissociation processes. Finally, the structural ambiguity and complex nature of the paramagnetic shifts does not allow us to accurately model metal-bound silicon atoms directly for any of the paramagnetic complexes herein.