Issue 43, 2021

Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR2)3}An(CCCPh2)] (An = U, Th; R = SiMe3)

Abstract

The reaction of [AnCl(NR2)3] (An = U, Th, R = SiMe3) with in situ generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR2)3}An(CH[double bond, length as m-dash]C[double bond, length as m-dash]CPh2)] (An = U, 1; Th, 2) in good yields after work-up. Deprotonation of 1 or 2 with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR2)3}An(CCCPh2)] (An = U, 3; Th, 4). The calculated 13C NMR chemical shifts of the Cα, Cβ, and Cγ nuclei in 2 and 4 nicely reproduce the experimentally assigned order, and exhibit a characteristic spin–orbit induced downfield shift at Cα due to involvement of the 5f orbitals in the Th–C bonds. Additionally, the bonding analyses for 3 and 4 show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single–triple–single-bond resonance structure (e.g., An–C[triple bond, length as m-dash]C–CPh2) predominates, the An[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CPh2 resonance form contributes, as well, more so for 3 than for 4.

Graphical abstract: Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR2)3}An(CCCPh2)]− (An = U, Th; R = SiMe3)

Supplementary files

Article information

Article type
Edge Article
Submitted
31 Aug. 2021
Accepted
02 Okt. 2021
First published
04 Okt. 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 14383-14388

Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR2)3}An(CCCPh2)] (An = U, Th; R = SiMe3)

G. T. Kent, X. Yu, G. Wu, J. Autschbach and T. W. Hayton, Chem. Sci., 2021, 12, 14383 DOI: 10.1039/D1SC04666G

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