A complete series of uranium(iv) complexes with terminal hydrochalcogenido (EH) and chalcogenido (E) ligands E = O, S, Se, Te

Abstract

Theoretical and experimental examination of the bonding situation in uranium complexes bearing terminal hydrochalcogenido and chalcogenido ligands.

Study of the histidine complex of uranium(IV): synthesis, spectrophotometric, magnetic and electrochemical properties

“…The complex absorbs maximum at the wavelengths 653 and 663 nm in the visible region. The metal to oxygen and metal to nitrogen coordination has been justified by our IR data and the previous studies [12,[19][20]. The novel compound has paramagnetic nature with two unpaired electrons.…”

“…The different modes of vibrations of the existing COO group in the complex gave rise to the peaks at 736, 659, and 561 cm 1 , which may correspond to its wagging, bending and rocking. The peaks at around 530 and 441 cm 1 may lead to coordinating sites such as oxygen and nitrogen; MO and MN, respectively [12,[19][20]. The peak at high energy (530 cm 1 ) may correspond to U-O coordination if we consider the electronegativity, availability of lone pair of electrons and opposite charges on uranium(IV) and oxygen ions that form strong bonding as compared to U-N.…”

“…Investigation of the ligation of radiotoxic elements such as uranium with compounds present in living organisms and especially in mammals is key knowledge for the development of methods to counter the effects of radiation poisoning. A recent interest drew the attention when a series of uranium(IV) complexes with two different types of ligands such as hydrochalcogenido and chalcogenido were synthesized to surface the effect of variation in the binding sites upon the molecular and electronic structure of the complexes [12]. The complexation of uranium(IV) with Me-naphthaquinoline was studied and its reactivity as a multielectron reducing agent to release two electrons through the cleavage of the C-C bond was reported [13].…”

Intrinsic reactivity of [OUCH]+: Apparent synthesis of [OUS]+ by reaction with CS2

“…The high reactivity of [O=U≡CH] + exhibited in our earlier study 7,11 led us to consider whether the species could be used as an intermediate to generate a product that includes a U–S bond. Interest in chalcogenido‐actinide (An) species, including those with discrete An–S bonds, comes in part from the fact that some separation strategies exploit the affinity of the f‐elements to chalcogenido ligands 12–14 . Study of complexes between actinides and chalcogenido ligands may also provide important information about the degree of covalency within 5f metal–ligand bonds.…”

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

“…There is intense current interest in the actinide‐ligand bonding, due mainly to ligand engagement in covalent bonding that has a remarkable influence on the extraction of actinides over lanthanides and/or group separation of actinides and increasing concerns about the participation level of 5f and 6d orbitals. [ 1‐7 ] Along this line, actinide‐ligand, such as actinide‐oxygen, [ 8‐11 ] actinide‐ nitrogen, [ 4,12‐13 ] actinide‐sulfur, [ 11,14‐15 ] actinide‐carbon [ 16‐20 ] and others [ 11,15,21‐23 ] have been extensively investigated both experimentally and theoretically, and further enhanced our understanding of bonding nature of actinide complexes. Although these molecular structures provide an insight into the performance that the 5f and 6d valence orbits play in the bonding, it is still a great challenge to synthesize novel actinide‐ligand complexes and investigate their bonding properties due to complicated electronic structure of actinide complexes.…”