Affiliation:
1. Department of Chemistry Fudan University Shanghai 200433 P. R. China
2. State Key Laboratory of Organometallic Chemistry, SIOC CAS Shanghai 200032 P. R. China
Abstract
AbstractDi‐ and multinuclear hafnium complexes bridged by ligands have been rarely reported. In this article, a novel 3,5‐disubstituted pyrazolate‐bridged ligand LH5 with two [N2N]2−‐type chelating side arms was designed and synthesized, which supported a series of dinuclear hafnium complexes. Dinuclear hafnium azides [LHf2(μ‐1,1‐N3)2(N3)2][Na(THF)4] 3 and [LHf2(μ‐1,1‐N3)2(N3)2][Na(2,2,2‐Kryptofix)] 4 were further synthesized and structurally characterized, featuring two sets of terminal and bridging azido ligands like jellyfishes. The reactivity of 3 under reduction conditions was conducted, leading to a formation of a tetranuclear hafnium imido complex [L1Hf2(μ1‐NH)(N3){μ2‐K}]2 5. DFT calculations revealed that the mixed imido azide 5 was generated via an intramolecular C−H insertion from a putative dinuclear HfIV‐nitridyl intermediate.
Funder
National Natural Science Foundation of China
Subject
General Chemistry,Biochemistry,Organic Chemistry