The interaction between the [(μ-L)3(L')3] cluster (L = CO, SO2, CNH; L = PH3, CNH) and a series of fragments X (Tl+, Hg(0), AuPH3+, CuPH3+ and AgPH3+) was studied using ab initio methodology. The calculations suggest that the complexes formed are stable. We have studied these complexes at the HF, MP2, B3LYP and PBE levels of theory. The magnitude of the interaction energies and -MPH3+ distances indicate a substantial covalent character of the bond. On the other hand, in [(μ-L)3(L")3]-X (Tl+ and Hg) the energy magnitudes are in the order of metallophilic interaction, which indicates that the dispersion and ionic terms are found as the main contribution to stability. These results have been confirmed by orbital diagrams. In addition, the Fukui index of electrophilic attack and electrophilicity index on the [(μ-L)3(L")3] clusters were used to explore possible sites that may play a role in chemical reactivity.