Nickel–gallium intermetalloid superatom clusters offer models of precise elemental atomic arrangements in composition-dependent mixed-metal assemblies; however, their interpretation becomes challenging in the case where several isobaric species are present within a single ligand-protected complex. In this work, the ligand-gated orthogonal probe mapping (LGOPM) strategy is applied to the series of intermetalloid clusters \(\mathrm{Ni}_{6+x}\mathrm{Ga}_{6+y}(\mathrm{Cp}^{\ast})_6\) with \(x+y\leq2\). The analysis utilizes the invariant \((\mathrm{NiCp}^{\ast})_6\) cage as a starting point with two independently defined probes, used to discriminate between accessible and protected inner-shell atoms. The main objective of this study is to determine whether it is possible to translate a mixture of isobaric Ni–Ga clusters into a resolution in terms of nickel and gallium site accessibility. The answer to this question is positive since carbon monoxide reaction allows one to select nickel-accessible compositions while the application of triisopropylsilyl acetylene photodissociation leads to isolation of the gallium derivatizable cluster. Thus, in the descriptor matrix, the \(\mathrm{Ni}_6\mathrm{Ga}_6\) and \(\mathrm{Ni}_6\mathrm{Ga}_7\) clusters belong to the group of cage-protected molecules; the \(\mathrm{Ni}_7\mathrm{Ga}_6\) and \(\mathrm{Ni}_7\mathrm{Ga}_7\) clusters belong to the class responding to carbon monoxide treatment while the \(\mathrm{Ni}_8\mathrm{Ga}_6\) cluster represents the photochemical gallium-labile molecule. Interpretations follow the major equations, figures, and tables, connecting indices, masses, spectroscopic, magnetism, and probe parameters with chemical phenomena.
