4.8 Article

Heterometallic Clusters with Multiple Rare Earth Metal-Transition Metal Bonding

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 15, Pages 5998-6005

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c01771

Keywords

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Funding

  1. National Natural Science Foundation of China [21772088, 91961116]
  2. Natural Science Foundation of Jiangsu Province [BK20200302]
  3. Fundamental Research Funds for the Central Universities [14380216]
  4. Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province (group program)

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This study presents the identification of a molecule containing multiple RE-Rh bonds, synthesized through reduction reaction and characterized by various experimental methods. Additionally, analogous species with different rare earth metals were constructed to investigate their structures and properties.
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[((CH2CH2NPPr2)-Pr-i)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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