Molecules containing actinide-nitrogen multiple bonds are of current interest as simple models for new actinide nitride nuclear fuels, and for their potential for the catalytic activation of inert hydrocarbon C-H bonds. Complexes with up to three uranium-nitrogen double bonds are now being widely studied, yet those with one thorium-nitrogen double bond are rare, and those with two are unknown. A new, simple mono(imido) thorium complex and the first bis(imido) thorium complex, K[Th(═NAr)N″3] and K2[Th(═NAr)2N″2], are readily made from insertion reactions (Ar = aryl, N″ = N(SiMe3)2) into the Th-C bond of the cyclometalated thorium amides [ThN″2(N(SiMe3)(SiMe2CH2))] and K[ThN″(N(SiMe3)(SiMe2CH2))2]. X-ray and computational structural analyses show a "transition-metal-like" cis-bis(imido) geometry and polarized Th═N bonds with twice the Wiberg bond order of the formally single Th-N bond in the same molecule.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.5b06630 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
ThCTi@(6)-C: Th═C Double Bond in a Mixed Actinide-Transition Metal Cluster.
J Am Chem Soc
January 2025
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China.
A thorium-carbon double bond that corresponds to the sum of theoretical covalent double bond radii has long been sought after in the study of actinide-ligand multiple bonding as a synthetic target. However, the stabilization of this chemical bond remains a great challenge to date, in part because of a relatively poor energetic matching between 5f-/6d- orbitals of thorium and the 2s-/2p- frontier orbitals of carbon. Herein, we report the successful synthesis of a thorium-carbon double bond in a carbon-bridged actinide-transition metal cluster, i.
View Article and Find Full Text PDFAlpha Atlas: Mapping global production of α-emitting radionuclides for targeted alpha therapy.
Nucl Med Biol
December 2024
Life Sciences Division, TRIUMF, BC V6T 2A3 Vancouver, British Columbia, Canada; Department of Chemistry, University of British Columbia, V6T 1Z1 Vancouver, British Columbia, Canada.
Targeted Alpha Therapy has shown great promise in cancer treatment, sparking significant interest over recent decades. However, its broad adoption has been impeded by the scarcity of alpha-emitters and the complexities related to their use. The availability of these radionuclides is often constrained by the intricate production processes and purification, as well as regulatory and logistical challenges.
View Article and Find Full Text PDFA flexible, antifreezing, and long-term stable cellulose ionic conductive hydrogel via one-step preparation for flexible electronic sensors.
Carbohydr Polym
March 2025
Key Laboratory of Thorium Energy, Shanghai Institute of Applied Physics, Chinese Academy of Science, No. 2019 Jialuo Road, Shanghai 201800, China.
Ionic conductive hydrogels have attracted great attention due to their good flexibility and conductivity in flexible electronic devices. However, because of the icing and water loss problems, the compatibility issue between the mechanical properties and conductivity of hydrogel electrolytes over a wide temperature range remains extremely challenging to achieve. Although, antifreezing/water-retaining additives could alleviate these problems, the reduced performance and complex preparation methods seriously limit their development.
View Article and Find Full Text PDFSynthesis and Evaluation of a Bifunctional Chelator for Thorium-227 Targeted Radiotherapy.
J Med Chem
January 2025
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Thorium-227 (Th) is an α-emitting radionuclide currently under investigation for targeted alpha therapy. Available chelators used for this isotope suffer from challenging multistep syntheses. Here, we present the synthesis and preclinical evaluation of a novel bifunctional chelator, SCN-Bn-DOTHOPO, which contains an isothiocyanate group that is suitable for conjugation to biological molecules.
View Article and Find Full Text PDFMetal-Metal Bonding in Tri-Actinide Clusters: A DFT Study of [AnCl] (z=1-6) and [AnClCp] (z=-2-+3; An=Ac, Th, Pa, U, Np, Pu).
Chemphyschem
November 2024
Department of Chemistry, School of Natural Sciences, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
The actinide-actinide bonding in tri-actinide clusters [An₃Cl₆] (An=Ac-Pu, z=1-6) and [An₃Cl₆Cp₃] (z=-2-+3; Cp=(η-CH)) is studied using density functional theory. We find 3-centre bonding similar to the tri-thorium cluster [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃{K(THF)₂}₂], as we previously reported (Nature 2021, 598, 72-75). The population of 3-centre molecular orbitals (3c-MOs) by zero, one or two electrons correlates with shortening of the An-An bond lengths, which also decrease with increasing actinide atomic number, consistent with the contraction of the actinide valence atomic orbitals.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!