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Updated: Sep 11, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Multi-electron redox reactivity of a thorium(ii) hydride synthon
Xianghui Shi1, Guorui Qin1, Peng Deng1,2
1State Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences No. 5625, Renmin Street Changchun 130022 China jhcheng@ciac.ac.cn.
None:
Molecular thorium complexes are dominated by stable tetravalent thorium, while subvalent thorium and the relevant synthons are very limited. Herein, we report that hydrogenolysis of the half-sandwich penta-arylcyclopentadienyl-supported thorium tribenzyl complex [(CpAr5)Th(p-CH2-C6H4-Me)3] (1) (CpAr5 = C5Ar5, Ar = 3,5-iPr2-C6H3) affords the double-sandwich bimetallic hydride complex [(CpAr5)Th(μ-H)]2 (2), in which one of the five aryl groups in the CpAr5 ligand is selectively reduced to a puckered di-anionic 1,4-cyclohexadienyl. Complex 2 can be regarded as a thorium(ii) hydride synthon, and exhibits unique redox-active reactivity towards various substrates. Complex 2 not only serves as the six-electron transfer reagent in the reduction of Te and N3SiMe3, leading to the formation of [(CpAr5)Th(THF)]2(μ-Te)3 (3) and [(CpAr5)Th(μ-N3)(μ-NSiMe3)]2 (4), but also promotes the four-electron reductive coupling of CS2 and benzonitrile accompanied by Th-H addition, resulting in the isolation of [(CpAr5)Th(μ-η2:η2-CS3)(μ-S)(μ-η4:η1-SCH[double bond, length as m-dash]CHS)Th(CpAr5)] (5) and [(CpAr5)Th(PhCN)2(μ-NCH2Ph){η1,κ3-NC(Ph)[double bond, length as m-dash]C(Ph)NC(Ph)[double bond, length as m-dash]NC(Ph)[double bond, length as m-dash]N}Th(CpAr5)] (6) respectively.
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