Organoactinides in catalytic transformations: scope, mechanisms and Quo Vadis

Abstract

The last decade has witnessed wonderful and remarkable advances in the chemistry of early actinides, providing information on not only the reactivity of these types of compounds in stoichiometric reactions but also their utilization in challenging catalytic processes. This canvas of knowledge allows the design of chemical reactivities to reach a high level of sophistication. As compared to early/late transition metal and lanthanide complexes, the actinides display complementary and in some cases real unique performances for similar organic transformations. The study of organoactinides allows us to design new chemical transformations due to their distinctive electronic structures, which feature a large coordination number exhibiting steric interactions. This review highlights the latest results obtained since 2008 on the catalytic activities of organoactinides. This review presents a brief introduction, and two main parts: (i) organoactinide mediated catalytic transformations of small molecules, including hydroelementation, coupling reactions, etc.; (ii) organoactinide catalysed polymerization and oligomerization reactions, including olefin, diene, cyclic ester and epoxide substrates. At the end, we present our Quo Vadis opinion and pose some challenging questions and our personal opinion regarding where this field should continue to develop.

Highly Active Ternary Nickel–Iron oxide as Bifunctional Catalyst for Electrochemical Water Splitting

“…[35][36][37][38][39] For instance, Zn-doped Ni 3 S 2 nanosheet array on nickel foam is reported to have an excellent activity as OER electrocatalyst in alkaline medium. [40] NiCo 2 P x coupled CNTs shows good activity for overall water splitting. [41] Compared to single 3d-transition metal based materials such as NiOx, CoOx, Fe 3 O 4, NiP, CoP, NiS, FeS, bi-metallic compounds such NiÀ Fe, NiÀ Co, FeÀ Co, etc.…”

Mo‐Doped Ni3S2 Nanowires as High‐Performance Electrocatalysts for Overall Water Splitting

“…[7][8][9] Currently, water splitting, involving the anodic oxygen evolution reaction (OER) and the cathodic hydrogen evolution reaction (HER), is widely regarded as a promising way to produce highly pure hydrogen. [10][11][12][13][14][15][16][17][18][19][20][21][22] However, the key challenge to developing such a technology lies in the exploration of efficient electrocatalysts for both the OER and HER with high catalytic performance and superior stability. To date, IrO 2 /RuO 2 and Pt are still considered as the state-of-the-art catalysts toward OER and HER; however, their low abundance and high costs greatly hinder their widespread applications.…”

Iron‐Doped LiCoO2 Nanosheets as Highly Efficient Electrocatalysts for Alkaline Water Oxidation

“…catalyst could improve the activity of catalyst for OER under alkaline conditions. [4,12,13,14,15] Doping can alter the adjacent atom electronic density, regulate the adsorption energy of active species and lower the kinetic energy barrier for water splitting. [4,14,16,17] More importantly, researchers have found that the incorporation of Fe ion into metal oxide and hydroxides could significantly reduce the overpotential and further improve the OER performances of electrocatalysts.…”