Shi Kaiying, Douair Iskander, Feng Genfeng, Wang Penglong, Zhao Yue, Maron Laurent, Zhu Congqing
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse, France.
J Am Chem Soc. 2021 Apr 21;143(15):5998-6005. doi: 10.1021/jacs.1c01771. Epub 2021 Apr 7.
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[(CHCHNPPr)RhCl(COD)]} with excess potassium-graphite. The oxidation state of Ce in 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.
尽管已经报道了一系列具有稀土（RE）金属-金属键的配合物，但具有多个RE-Rh键的配合物尚属未知。在此，我们展示了首个含有多个RE-Rh键的分子实例的鉴定。通过用过量的钾-石墨还原d-f异金属分子簇Ce{N[(CHCHNPPr)RhCl(COD)]}合成了具有多个Ce-Rh键的配合物。通过X射线光电子能谱、磁性和理论研究（DFT和CASSCF）证实， 中Ce的氧化态似乎是Ce(III)和Ce(IV)的混合物。为作比较，还构建了具有多个La(III)-Rh和Nd(III)-Rh键的类似物种。本研究为构建具有多个RE金属-金属键的配合物以及研究其潜在性质和应用提供了一条可能的途径。
