Walking Metals in d 8 ⋅⋅⋅d 8 Hetero‐bimetallic Complexes: An Original Dynamic Phenomenon

In the course of our investigations on polymetallic complexes derived from 1,3‐bis(thiophosphinoyl)indene (Ind(Ph 2 PS) 2 ), we observed original fluxional behavior and report herein a joint experimental/computational study of this dynamic process. Starting from the indenylidene chloropalladate species [Pd{Ind(Ph 2 PS) 2 }Cl] − ( 1 ), the new Pd II ⋅⋅⋅Rh I hetero‐bimetallic pincer complex [PdCl{Ind(Ph 2 PS) 2 }Rh(nbd)] ( 2 ; nbd=2,5‐norbornadiene) was prepared. X‐ray crystallography and DFT calculations substantiate the presence of a d 8 ⋅⋅⋅d 8 interaction. According to multinuclear variable‐temperature NMR spectroscopic experiments, the pendant {Rh(nbd)} fragment of 2 readily shifts in solution at room temperature between the two edges of the SCS tridentate ligand. To assess the role of the pincer‐based polymetallic structure on this fluxional behavior, the related monometallic Rh complex [Rh{IndH(Ph 2 PS) 2 }(nbd)] ( 3 ) was prepared. No evidence for a metal shift was observed in that case, even at high temperature, thus indicating that inplane pincer coordination to the Pd center plays a crucial role. The previously described Pd II ⋅⋅⋅Ir I bimetallic complex 4 exhibited fluxional behavior in solution, but with a significantly higher activation barrier than 2 . This finding demonstrates the generality of this metal‐shift process and the strong influence of the involved metal centers on the associated activation barrier. DFT calculations were performed to shed light onto the mechanism of such metal‐shift processes and to identify the factors that influence the associated activation barriers. Significantly different pathways were found for bimetallic complexes 2 and 4 on one hand and the monometallic complex 3 on the other hand. The corresponding activation barriers predicted computationally are in very good agreement with the experimental observations.