Complexes of uranium(V)chloride with nitrogen donor ligands

A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl5− and UCl5

“…The ADE of 4.73 eV at the CCSD(T)/SO level is in excellent agreement with the experimental value of 4.76 eV ( Table 2). [13,[18][19][20]26] However, the results were not always consistent due to the assumptions about the geometry of UCl 5 . The 350 cm À1 v s A C H T U N G T R E N N U N G (U À Cl ax ) vibrational frequency was exactly the value used to derive the bond dissociation energy D8 (Cl 4 U À Cl) by Lau and Hildenbrand.…”

“…[13] There have been significant previous efforts to estimate the vibrational frequencies of UCl 5 , as well as the product of its three principal moments of inertia. [13,[18][19][20]26] However, the results were not always consistent due to the assumptions about the geometry of UCl 5 . [26] Therefore, the current findings lend considerable credence to the optimized structure and C 4v symmetry of UCl 5 .…”

“…[17][18][19][20] Spectroscopic information of isolated UCl 5 and UCl 5 À complexes in the gas phase would be valuable to validate the relativistic quantum chemistry methods developed to account for the f electrons in chemical bonding. [17][18][19][20] Spectroscopic information of isolated UCl 5 and UCl 5 À complexes in the gas phase would be valuable to validate the relativistic quantum chemistry methods developed to account for the f electrons in chemical bonding.…”

“…to strongly influence the electronic properties of the UCl 5 ·nL species. [17][18][19][20] Spectroscopic information of isolated UCl 5 and UCl 5 À complexes in the gas phase would be valuable to validate the relativistic quantum chemistry methods developed to account for the f electrons in chemical bonding. [21][22][23][24][25] In particular, U is in its + 5 oxidation state in UCl 5 with a ground electronic configuration of [Rn]5f 1 , making it an ideal system to compare with theoretical calculations.…”

Utility of redox-active ligands for reversible multi-electron transfer in uranyl(vi) complexes

“…Although it is eventually possible for U 5+ to be formed, this reaction takes place only under rather exotic environments, such as in molten salts or thionyl chloride. 56 Therefore, it is difficult to employ the rich electrochemistry of U alone to establish reversible multi-step redox processes as long as the redox reactions occur at the U VI O 2 2+ center. In this context, we wondered if the introduction of a redox-active ligand would be an effective alternative approach to the multi-electron chemistry of the U VI O 2 2+ complexes.…”