Wen Qingqing, Rajeshkumar Thayalan, Maron Laurent, Leng Xuebing, Chen Yaofeng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
LPCNO, CNRS, & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077, Toulous, France.
Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202200540. doi: 10.1002/anie.202200540. Epub 2022 Apr 27.
The trivalent rare-earth metal hydrido and imido complexes are of versatile reactivity, and many such complexes have been synthesized. However, no example of a rare-earth metal complex bearing both hydrido- and imido-ligands has been reported. Herein, we report the first rare-earth metal complex bearing both hydrido- and imido-ligands, namely a hydrido- and imido-bridged dinuclear ytterbium(III) complex. The complex was synthesized via an unprecedented redox reaction of divalent rare-earth metal hydrido complex with azido compound. DFT calculation indicated that the N release from azido compound in the presence of ytterbium(II) is a kinetically facile process because of the cooperative effects of the two metal centers. The reactivity of the hydrido- and imido-bridged dinuclear ytterbium(III) complex was also explored, which showed the redox, addition and σ-bond metathesis reactivities.
三价稀土金属氢化物和亚胺基配合物具有多种反应活性，并且已经合成了许多此类配合物。然而，尚未报道过同时含有氢化物和亚胺基配体的稀土金属配合物的实例。在此，我们报道了首例同时含有氢化物和亚胺基配体的稀土金属配合物，即一种氢化物和亚胺基桥联的双核镱（III）配合物。该配合物是通过二价稀土金属氢化物配合物与叠氮化合物发生前所未有的氧化还原反应合成的。密度泛函理论计算表明，在镱（II）存在下，叠氮化合物释放氮的过程在动力学上是容易的，这是由于两个金属中心的协同作用。还探索了氢化物和亚胺基桥联的双核镱（III）配合物的反应活性，其表现出氧化还原、加成和σ键复分解反应活性。
