ABSTRACT: To understand the synergistic catalytic effect on the thermal degradation of Ammonium Perchlorate (AP) when the metal fragments are in the same molecule or not, we compared three reported compounds: [(Cp*)2Ni] (1), [(Cp*)2Ru] (2), and [Cp*Ni-s-Ic’-RuCp*] (3), as potential burning rate catalysts. We conducted a differential scanning calorimetry (DSC) analysis of compound (3), which showed an increase in the high-temperature decomposition (HTD) of AP to 418 ºC and a decrease in the energy release to 938 J·g-1. These results were compared to those of the different metallocenes, namely (1) (HTD: 434 ºC and 1300 J·g-1), (2) (HTD: 361 ºC and 1828 J·g-1), and the mixture of (1+2) (HTD: 354 ºC and 2054 J·g-1). Our results suggest that the mixture of metallocenes is a suitable and competitive alternative to be used as an enhancer of solid composite propellants. In addition, cyclic voltammetry is used to investigate the electrochemical processes of compounds (1), (2), and (3). The electrochemically active species exhibit noteworthy oxidation peaks, revealing electronic communication between the three different compounds in the cases of (1), (2), and (3), as evidenced by the results obtained from the analysis.