Issue 47, 2021

Synthesis of a heterobimetallic actinide nitride and an analysis of its bonding

Abstract

Reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] (R = SiMe3) with 1 equiv. of [U(NR2)3(NH2)] (1) in THF, in the presence of 18-crown-6, results in formation of a bridged uranium–thorium nitride complex, [K(18-crown-6)(THF)2][(NR2)3UIV(μ-N)ThIV(NR2)3] (2), which can be isolated in 48% yield after work-up. Complex 2 is the first isolable molecular mixed-actinide nitride complex. Also formed in the reaction is the methylene-bridged mixed-actinide nitride, [K(18-crown-6)][K(18-crown-6)(Et2O)2][(NR2)2U(μ-N)(μ–κ2-C,N–CH2SiMe2NR)Th(NR2)2]2 (3), which can be isolated in 34% yield after work-up. Complex 3 is likely generated by deprotonation of a methyl group in 2 by [NR2], yielding the new μ-CH2 moiety and HNR2. Reaction of 2 with 0.5 equiv. of I2 results in formation of a UV/ThIV bridged nitride, [(NR2)3UV(μ-N)ThIV(NR2)3] (4), which can be isolated in 42% yield after work-up. The electronic structure of 4 was analyzed with EPR spectroscopy, SQUID magnetometry, and NIR-visible spectroscopy. This analysis demonstrated that the energies of 5f orbitals of 4 are largely determined by the strong ligand field exerted by the nitride ligand.

Graphical abstract: Synthesis of a heterobimetallic actinide nitride and an analysis of its bonding

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Sept. 2021
Accepted
13 Nov. 2021
First published
15 Nov. 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, 15519-15527

Synthesis of a heterobimetallic actinide nitride and an analysis of its bonding

S. L. Staun, G. Wu, W. W. Lukens and T. W. Hayton, Chem. Sci., 2021, 12, 15519 DOI: 10.1039/D1SC05072A

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