We started our study with the reaction between (syn--C,O-1a)Ni(CO)2 (2a) and an equimolar amount of Al(C6F5)3(tol)0.5, which resulted in the selective formation of heterobimetallic Ni/Al complex 3a in 90% yield (Figure ). We also confirmed that the Al(C6F5)3-mediated rotation of N-phosphinoyl moieties in 2b-d afforded the corresponding heterobimetallic Ni/Al complexes (3b-d) in good-to-high yield. The molecular structures of 3ad were fully characterized using NMR and ATR-infrared (IR) absorption spectroscopy as well as SC-XRD analysis (vide infra). Subsequently, we treated 3a with slightly excess amounts of 4dimethylaminopyridine (DMAP) and confirmed the quantitative regeneration of 2a with the concomitant formation of the adduct DMAP-Al(C6F5)3 (Figure ). These results demonstrated that the interconversion between 2a and 3a can be successfully mediated by the addition/removal of Al(C6F5)3.