Über tricyclopentadienyluran(III) und seine addukte mit tetrahydrofuran, cyclohexylisonitril und l-nicotin

A DFT and experimental investigation of the electron affinity of the triscyclopentadienyl uranium complexes Cp3UX

“…Moreover, MO diagrams and population analyses permitted to understand the evolution of EA with the nature of the X ligand, especially with its electron donating capacity. Indeed, the electron affinities as well as the LUMO energies decrease with the electron-donating strength of X according to Cl < BH 4 Tetrahydrofuran (Aldrich) was stored under vacuum over sodium and benzophenone and transferred directly into the electrochemical cell by simple condensation (static vacuum method). Tetrabutylammonium hexafluorophosphate (Fluka, electrochemical grade), used without further purification, was dried under vacuum.…”

“…To the best of our knowledge, there is only one theoretical investigation of the EAs of actinide compounds which concerns the fluoroketimide complexes Cp* 2 U(-N=CMeR) 2 (R = 4-F-C 6 H 4 or C 6 F 5 ), 12 while a relatively few voltammetry experiments on triscyclopentadienyl and bispentamethylcyclopentadienyl complexes led to the observation of the U(III)/U(IV), U(IV)/U(V) and U(V)/U(VI) redox systems, depending on the nature of the different ligand sets. 12- 20 Here we present relativistic DFT calculations of the EAs of Cp 3 UX (X = Cl, BH 4 ,S P h ,S i Pr, O i Pr) complexes. In order to compare computed EAs to electrochemical experimental data obtained in solution, solvent effects are taken into account using the Conductor-like Screening Model (COSMO) approach.…”

Observation de la résonance paramagnétique électronique dans les composés organométalliques de l'uranium (III)

“…Par contre il apparait que l'U1ll est stabilise par les ligands de type C,H, (note Cp). C'est ainsi que l'adduit UCp3.THF ou THF designe le tetrahydrofurane est obtenu facilement par plusieurs methodes a partir de UCp,Cl ou UCp3-alkyl (1)(2)(3)(4). De m2me un trimere [(Me,C,),U-Cl], a CtC isole par Marks et coll.…”

Electrochemical and spectroscopic investigations of uranium(III) with N,N,N′,N′-tetramethylmalonamide in DMF

“…Few reports have appeared on the U(III) complex with Werner-type ligands except for a pyridine-delivative ligand [12] and N,N,N ,N -tetramethylmalonamide [19], whereas a large number of studies appear on non-Werner-type complexes of U(III), e.g. UI 3 (THF) 4 (THF: tetrahydrofuran) [22], UCl 3 (THF) x [23], Cp 3 U, Cp 3 U*THF [24] and U[N(SiMe 3 ) 2 ] 3 [25], or those of the U(IV) which undergo reversible reactions of U(IV)/U(III), e.g. UCp 2 Cl 2 [26].…”