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.
Angew Chem Int Ed Engl. 2023 May 15;62(21):e202303379. doi: 10.1002/anie.202303379. Epub 2023 Apr 18.
Although examples of multiple bonds between actinide elements and main-group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis-[M U M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine-bridged heterometallic complexes [{U{N(CH )(CH CH NP Pr ) }(Cl) [(μ-Cl)M(COD)] }] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U-M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U M double dative bonds in these complexes. This study not only enriches the U M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.
虽然镧系元素和主族元素之间的多重键的例子相当常见，但由于其合成困难，镧系元素和过渡金属之间的多重键的研究极为罕见。在这里，我们报告了第一个具有顺式-[M U M]核心（M=Rh，Ir）的铀分子配合物的实例，其表现出两个 M U 双 dative 键连接到单个 U 中心的前所未有的排列。这些配合物是通过氯桥杂金属配合物[{U{N(CH )(CH CH NP Pr ) }(Cl) [(μ-Cl)M(COD)] }]（M=Rh，Ir）与 MeMgBr 或 MeLi 的反应制备的，这是一种构建具有 U-M 多重键的物种的新方法。包括色散在内的理论计算证实了这些配合物中存在两个 U M 双键。这项研究不仅丰富了 U M 多重键化学，还为探索镧系元素的键合提供了新的机会。
