Rare-earth metal and actinide organoimide chemistry

Abstract

Elaborate synthesis schemes pave the way to f-element and group 3 complexes with multiply bonded imido ligands displaying intriguing reactivity.

Divergent uranium- versus phosphorus-based reduction of Me3SiN3 with steric modification of phosphido ligands

“…One of the most investigated substrates for interrogating U(III) reaction chemistry has been organic azides. 15 This twoelectron reduction typically is done by the metal centre to form a U(V) imido. There are limited examples of U(IV) oxidation to U(VI), [16][17][18][19][20][21][22][23] all of them involving oxo-or imido-delivering agents.…”

Alkaline Earth Metal Imido Complexes with Doubly Deprotonated Amidine and β‐Diketimine Ligands

“…While transition metal or lanthanide imido complexes have found a broad interest in bond activation and catalysis, access to alkaline earth (Ae) metal imido complexes has been challenging . The simplest Ae=NH systems have been studied as high capacity, reversible, hydrogen storage materials but are insoluble salts .…”

Redox and structural properties of accessible actinide(ii) metallocalixarenes (Ac to Pu): a relativistic DFT study

“…In-depth understanding of fundamental concepts like oxidation state, bonding and electronic structures has helped to reveal structures of related complexes and properties and rationalize existing/potential applications. [1][2][3][4][5] In this respect, Evans and coworkers conducted a pioneering work in that an isolable U(II) complex, [K(2.2.2-cryptand)]$[UL 3 ] (L 3 stands for three Cp 0 (C 5 H 4 SiMe 3 ) ligands, in Chart 1), was crystallographically identi-ed. 6 This extended uranium oxidation state to +II with respect to commonly recognized +III to +VI.…”

“…The redox property is of great importance in manipulating the actinide chemistry of coordination, energy and environment, for it is involved in processing nuclear fuel, spent fuel and nuclear waste as well as remedying environmental contamination that highly radiotoxic actinides create. [1][2][3][4][5]23 However, relevant techniques remain greatly challenging. For example, reports about reduction potentials of U(II) complexes are very rare, which may be restricted by experimental difficulties such as safe handling of high radioactivity, sample stability/scarcity and applicable solvent shortage.…”

“…It also plays a signicant role in determining electronic structures and bonding. Recently, a versatile trans-calix [2]pyrrole [2]benzene (H 2 L 2 , Chart 1) 35 has been exploited to fabricate complexes of An III and An VI (An ¼ Th, U and Np) 18,[36][37][38] and even a Np II one 18 although being unstable chemically. Apparently, H 2 L 2 is able to stabilize various valence and sorts of actinide.…”