南京大学朱从青团队报道了多个稀土金属-过渡金属键合的异质金属团簇。 相关研究成果于2021年4月7日发表于国际一流学术期刊《美国化学会杂志》。

虽然已经报道了一系列具有稀土金属-金属键的配合物，但具有多个稀土-铑键的配合物尚不清楚。

该文中，研究人员给出了第一个含有多个RE–Rh键的分子的例子。用过量钾石墨还原d-f杂金属分子簇Ce{N[（CH2CH2NPiPr2）RhCl（COD）]3}合成了具有多个Ce-Rh键的配合物。X射线光电子能谱、磁学和理论研究（DFT和CASSCF）证实了Ce在3a中的氧化状态为Ce（III）和Ce（IV）的混合物。为了比较，研究人员还构建了具有多个La（III）–Rh和Nd（III）–Rh键的类似物种。

该研究为构建具有多个稀土金属-金属键的配合物提供了一条可能的途径，并对其潜在的性质和应用进行了研究。

据了解，虽然有一系列稀土金属-金属键配合物的报道，但含有多种稀土-铑键的配合物还不清楚。

附：英文原文

Title: Heterometallic Clusters with Multiple Rare Earth Metal–Transition Metal Bonding

Author: Kaiying Shi, Iskander Douair, Genfeng Feng, Penglong Wang, Yue Zhao, Laurent Maron, Congqing Zhu

Issue&Volume: April 7, 2021

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.

DOI: 10.1021/jacs.1c01771

Source: https://pubs.acs.org/doi/10.1021/jacs.1c01771