F-element Chemistry Research Articles

Catching Gaseous SO2 in Cone-Type Lanthanide Complexes: An Unexpected Coordination Mode for SO2 in f-Element Chemistry

Easy come, easy go: the first molecular SO(2) complexes of the lanthanides (Ln=Sm, Eu) have been prepared. The compounds can reversibly coordinate gaseous SO(2). Concomitant with the addition and removal of SO(2), the color of the complexes changes reversibly. The structures of the SO(2) compounds could be confirmed in solution and in the solid state.

Highly resolved synchrotron-based investigations related to nuclear waste disposal

ABSTRACTSynchrotron-based X-ray techniques are used increasingly to characterize actinide element speciation in heterogeneous media related to nuclear waste disposal safety. Especially techniques offering added temporal, spatial and energy resolved information are advancing our understanding of f-element physics and chemistry in general and of actinide element waste disposal in particular. Examples of investigations of uranium containing systems using both highly (energy) resolved X-ray emission spectroscopy (HRXES) techniques and spatially resolved techniques with focused X-ray beams are presented in this paper: polarization dependent partial fluorescence yield X-ray absorption near edge structure (PD-PFY-XANES) spectroscopic studies of a single Cs2UO2Cl4 crystal, which experimentally reveal a splitting of the σ, π, and δ components of the 6d valence states [1], and characterization of UO2/Mo thin films prepared on different substrates using a combination of techniques (2D and 3D micro- and nano-X-ray fluorescence, XANES and both holographic and ptychographic tomography).

F‐Element Chemistry (Eur. J. Inorg. Chem. 18/2010)

European Journal of Inorganic ChemistryVolume 2010, Issue 18 p. 2553-2553 Editorial f-Element Chemistry (Eur. J. Inorg. Chem. 18/2010) Gerd Meyer, Gerd MeyerSearch for more papers by this author Gerd Meyer, Gerd MeyerSearch for more papers by this author First published: 17 June 2010 https://doi.org/10.1002/ejic.201090051AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume2010, Issue18Special Issue: f-Element ChemistryJune 2010Pages 2553-2553 RelatedInformation

Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C(5)Me(5))(2)Yb, abbreviated as Cp*(2)Yb. Data used to support this claim include ytterbium valence measurements using Yb L(III)-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f(13)(pi*)(1), where pi* is the lowest unoccupied molecular orbital of the bipyridine or diazabutadiene ligands, and a closed-shell singlet f(14) component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

Monomeric f-element chemistry with sterically encumbered allyl ligands

A new class of allyl-lanthanide salts of the type [K(thf) 4][(C 3H 3(SiMe 3) 2) 3LnI] (Ln=Ce, Pr, Nd, Gd, Tb, Dy, Er) have been prepared and isolated by reaction of three equivalents of the 1,3-bis(trimethylsilyl)allyl anion with LnI 3. The neutral complex [C 3H 3(SiMe 3) 2] 3Nd(thf) has been isolated from the reaction of the triflate complex Nd(O 3SCF 3) 3 with three equivalents of the 1,3-bis(trimethylsilyl)allyl anion. These complexes have been structurally characterized using single crystal X-ray diffraction.

Sterische Cyclopentadienyl‐Äquivalente in der Chemie der f‐Elemente: Monomere, homoleptische Lanthanid(III)‐tris[N,N′‐bis(trimethylsilyl)‐benzamidinate

Steric Cyclopentadienyl Equivalents in f‐Element Chemistry: Monomeric, Homoleptic Lanthanide(III) Tris[N,N′‐bis(trimethylsilyl)benzamidinates]Anhydrous lanthanide trichlorides react with N‐silylated sodium benzamidinates, Na[4‐RC6H4C(NSiMe3)2], (1a–d), to give the monomeric, homoleptic lanthanide(III) benzamidinates [4‐RC6H4C(NSiMe3)2]3Ln (2–23, R = H, MeO, CF3, Ph). The molecular structure of [4‐MeOC6H4C(NSiMe3)2]3Pr (11) has been determined by X‐ray diffraction. Absorption and emission measurements reveal that the three benzamidinate ligands produce an unusually large crystal field which is comparable with that of cyclopentadienyl.