[U(Tp(Me2))2(bipy˙)], a uranium(III) complex with a radical bipyridine ligand which has magnetic properties with contributions from both the ligand and the metal, presents slow relaxation of the magnetisation at low temperatures, already under zero static magnetic field, and energy barriers slightly above the non-radical analogues.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/c4cc04486j | DOI Listing |
Inorg Chem
May 2024
Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.
We introduce the boryloxide ligand {(HCNDipp)BO} (NBO, Dipp = 2,6-di-isopropylphenyl) to actinide chemistry. Protonolysis of [U{N(SiMe)}] with 3 equiv of NBOH produced the uranium(III) tris(boryloxide) complex [U(NBO)] (). In contrast, treatment of UCl with 3 equiv of NBOK in THF at room temperature or reflux conditions produced only [U(NBO)(Cl)(THF)] () with 1 equiv of NBOK remaining unreacted.
View Article and Find Full Text PDFChem Commun (Camb)
April 2024
H. C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
A uranium(III) silylate complex [K(DME)][UI{(Si(SiMe)SiMe)O}] (1) was stabilized by the addition of 18-crown-6, forming [K(18-crown-6)][UI{(Si(SiMe)SiMe)O}] (1-crown). Crystallization under multiple conditions resulted in three distinct molecular structures. Compound 1-crown was further characterized in the solution state H, C, and Si NMR spectroscopy, and electronic absorption spectroscopy.
View Article and Find Full Text PDFInorg Chem
May 2024
Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
U(IV) cyclometalated complexes have shown rich reactivity, but their low oxidation state analogues still remain rare. Herein, we report the isolation of [K(2.2.
View Article and Find Full Text PDFJ Am Chem Soc
January 2024
Department of Chemistry, University of California, Berkeley, California 94720-1460, United States.
Dihydrogen complexation, a phenomenon with robust precedent in the transition metal series, is spectroscopically detected for a uranium(III) complex and thereby extended for the first time to the 5f series. The vacant coordination site and low valence of (CHSiMe)U prove to be key to the reversible formation of (CHSiMe)U-H (complex ), and the paramagnetism of the f center facilitates the detection of complex by NMR spectroscopy. Density functional theory calculations reveal that the delocalization of the 5f electron density from (CHSiMe)U onto the side-on dihydrogen ligand is crucial to complex formation, an unusual bonding situation for an actinide acid-base complex.
View Article and Find Full Text PDFChem Sci
November 2023
Insititut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL) 1015 Lausanne Switzerland
Understanding the role of multimetallic cooperativity and of alkali ion-binding in the second coordination sphere is important for the design of complexes that can promote dinitrogen (N) cleavage and functionalization. Herein, we compare the reaction products and mechanism of N reduction of the previously reported K-bound dinuclear uranium(iii) complex, [K{[U(OSi(OBu))](μ-O)}], B, with those of the analogous dinuclear uranium(iii) complexes, [K(2.2.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!