Heterometallic Clusters with Multiple Rare Earth Metal−Transition Metal Bonding

Kaiying ShiIskander DouairGenfeng FengPenglong WangYue ZhaoLaurent Maron*Congqing Zhu*

Abstract: Although a series of complexes with rare earth (RE) metal–metal bonds have been reported, complexes which have multiple RE–Rh bonds are unknown. Here we present the identification of the first example of a molecule containing multiple RE–Rh bonds. The complex with multiple Ce–Rh bonds was synthesized by the reduction of a d–f heterometallic molecular cluster Ce{N[(CH2CH2NPiPr2)RhCl(COD)]3} with excess potassium-graphite. The oxidation state of Ce in 3a appears to be a mixture of Ce(III) and Ce(IV), which was confirmed by X-ray photoelectron spectroscopy, magnetism, and theoretical investigations (DFT and CASSCF). For comparison, the analogous species with multiple La(III)–Rh and Nd(III)–Rh bonds were also constructed. This study provides a possible route for the construction of complexes with multiple RE metal–metal bonds and an investigation of their potential properties and applications.

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