Jellyfish-type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity.

ABSTRACT

Di- 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 [N2 N]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 [L1 Hf2 (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.