Heterometallic d8 -d10 Coupling of Rh(I) and M(0) (M=Pd, Pt) in a Sandwich Framework of π-Conjugated Ligands.

A heterometallic M-M' bond formation is a key to construct atomically precise bimetallic clusters and materials. However, it is sometimes not straightforward to construct a heterometallic M-M' bond through conventional methods including redox condensation. Here, we found that a sandwich framework of π-conjugated unsaturated hydrocarbon ligands provides a unique coordination environment that facilitates unusual coupling of d8 RhI and d10 M0 (M=Pd, Pt). The molecular orbital analysis showed that the electron-accepting ability of the sandwich framework through back-donation allows the formation of a dσ-type Rh-Pd bond in a (d-d)18 electron system.