Organometallic Neptunium Chemistry

Abstract

Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer have been fully characterized. Yet, increasingly, combined synthetic/spectroscopic/computational studies are demonstrating how covalently bonding, soft, carbocyclic organometallic ligands provide an excellent platform for advancing the fundamental understanding of the differences in orbital contributions and covalency in f-block metal-ligand bonding. Understanding the subtleties is the key to the safe handling and separations of the highly radioactive nuclei. This review describes the complexes that have been synthesized to date and presents a critical assessment of the successes and difficulties in their analysis and the bonding information they have provided. Because of increasing recent efforts to start new Np-capable air-sensitive inorganic chemistry laboratories, the importance of radioactivity, the basics of Np decay and its ramifications (including the radiochemical synthesis of one organometallic compound), and the available anhydrous starting materials are also surveyed. The review also highlights a range of instances in which important differences in the chemical behavior between Np and its closest neighbors, uranium and plutonium, are found.

Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour

“…Thus, Kaltsoyannis reviewed the theoretical approacht ot ransuranic computational chemistry. [13] Ephritikhine highlighted the rich uranium and thorium Cp chemistry [14] whereast he organometallic neptunium chemistry was reviewedb yA rnold et al [15] followed by ar eview from Walter on the organometallic chemistry of the actinides. [16] Recently, Abergel and Kozimors ummarised innovative f-elementc helating strategies in aspecial issue of Inorganic Chemistry.…”

Novel organotin (IV) complexes derived from 4,4′‐oxybisbenzoic acid: synthesis, structure, in vitro cytostatic activity and binding interaction with BSA

“…In recent years, organometallic self‐assembly based on combinations of metal centers and bridging ligands has become a powerful tool for the construction of novel compounds possessing various architectures and physical properties . Organotin compounds, as an important part of organometallic compounds, have obtained by reactions of organotin chlorides, oxides, hydroxides, and oxide hydroxides with protic acids (carboxylic acids, phosphinic acids, phosphonic acids and sulfonic acids) .…”

Future Directions for Transuranic Single Molecule Magnets

“…Indeed, elements of the 5f block potentially combine single-ion anisotropy as large as in rare earths with exchange interactions strong enough to couple magnetic centres in polynuclear complexes. Moreover, contrary to rare earths, actinides can be stabilized in different oxidation states and are prone to form covalent bonds, thus offering an unparalleled chemical versatility in designing the molecular structure [9][10][11]. However, all actinide-based SMMs reported up to now perform significantly worse than the best rare-earth ones, in terms of both relaxation barrier and blocking temperature [12].…”