Heterometallic d8-d10 Coupling of Rh(I) and M(0) (M=Pd, Pt) in a Sandwich Framework of pπ-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 pi-conjugated unsaturated hydrocarbon ligands provides a unique coordination environment that facilitates unusual coupling of d(8) Rh-I and d(10) M-0 (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 d sigma-type Rh-Pd bond in a (d-d)(18) electron system.

Automated summary

The formation of a heterometallic M-M' bond is crucial in constructing atomically precise bimetallic clusters and materials. By utilizing a sandwich framework of pi-conjugated unsaturated hydrocarbon ligands, a unique coordination environment is created that facilitates the unusual coupling of d(8) Rh-I and d(10) M-O (M=Pd, Pt), allowing the formation of a d sigma-type Rh-Pd bond.