The differing structures and reactivities of "GaI" samples prepared with different reaction times have been investigated in detail. Analysis by FT-Raman spectroscopy, powder X-ray diffraction, Ga-71 solid-state NIMR spectroscopy, and I-127 nuclear quadrupole resonance (NQR) provides concrete evidence for the structure of each "GaI" sample prepared. These techniques are widely accessible and can be implemented quickly and easily to identify the nature of the "GaI" in hand. The "GaI" prepared from exhaustive reaction times (100 min) is shown to possess Ga2I3 and an overall formula of [Ga-0](2)[Ga+](2)[Ga2I62-], while the "GaI" prepared with the shortest reaction time (40 min) contains GaI2 and has the overall formula [Ga-0](2)[Ga+][GaI4-]. Intermediate "GaI" samples were consistently shown to be fractionally composed of each of these two preceding formulations and no other distinguishable phases. These "GaI" phases were then shown to give unique products upon reactions with the anionic bis(phosphino)borate ligand class. The reaction of the early-phase "GaI" gives rise to a unique phosphine Ga(II) dimeric coordination compound (3), which was isolated reproducibly in 48% yield and convincingly characterized. A base-stabilized GaI -> GaI3 fragment (4) was also isolated using the late-phase "GaI" and characterized by multinuclear NMR spectroscopy and X-ray crystallography. These compounds can be considered unique examples of low-oxidation-state P -> Ga coordination compounds and possess relatively long Ga-P bone lengths in the solid-state structures. The anionic borate backbone therefore results in interesting architectures about gallium that have not been observed with neutral phosphines.