To gain further insights into the differences between the structural analogs, Natural bond orbital (NBO) analysis was performed. By transforming a given wave function into localized form (i.e. a molecular orbital), NBOs describe electronic structures in terms of localized two-centre bonds and lone pairs, relating computed values to Lewis structure representations. The NBO contribution to VZZ from the Ga-N bonding orbital of py in 1-py (-1.49 a.u.) is significantly more negative than the NBO contribution to VZZ arising from the interaction of the oxygen atom of TPPO with the Ga centre in 1- TPPO (-1.29 a.u.), which is more negative than the NBO contribution to VZZ from the lone pair of oxygen of the THF moiety of 1-THF (-1.08 a.u). This highlights the correlation between the extent of donation from the neutral donor and the magnitude of VZZ, while the variation in VZZ found for the series of molecules show the pronounced effect of small changes in immediate coordination environment on the EFG tensors (vide infra), highlighting that CQ and η provide unique tools to distinguish similar coordination environments.