The Coulomb explosion of clusters is known to be an efficient source for producing multiply charged ions through an enhanced ionization process. However, the factors responsible for obtaining these high charge states have not been previously explored in detail and remain poorly understood. By comparing intensity-resolved visible laser excitation experiments with semi-classical theory over a range spanning both multiphoton and tunneling ionization regimes, we reveal the mechanism in which extreme ionization proceeds. Under laser conditions that can only singly ionize individual molecules, ammonia clusters generate ions depleted of all valence electrons. The geometries of the molecular orbitals are revealed to be important in driving the ionization, and can be entirely emptied at the energy requirement for removal of the first electron in the orbital. The results are in accord with non-sequential ionization arising from electrons tunneling from three separate molecular orbitals aided through the ionization ignition mechanism.