Progress in the chemistry of molecular actinide-nitride compounds

Abstract

This review covers the rapid progress that was made over the past decade in the chemistry of actinide nitrides with a focus on uranium terminal and bridging nitrides, their synthesis and reactivity, and a few recent breakthroughs with thorium.

Multimetallic Uranium Nitride Cubane Clusters from Dinitrogen Cleavage

“…Molecular nitride compounds were identified as important intermediates in the biological and industrial conversion of dinitrogen into ammonia and N-containing organic compounds, but the mechanism of N 2 cleavage to nitride remains unclear. − Because of their relevance as a precursor and model of inorganic uranium nitrides and in the understanding of uranium-ligand multiple bonding, the chemistry of molecular uranium nitride compounds has witnessed significant advances in the last 10 years. , The synthesis of molecular cluster analogs of uranium mononitride (UN) is important for modeling the properties of bulk UN, but most molecular uranium nitrides reported so far show a low nitride content (1 or 2 N 3– ligands) − with only two larger U 4 N 4 and U 8 N 4 clusters containing four nitride ligands. , Moreover, despite inorganic uranium compounds being reported to be efficient catalysts for N 2 conversion to ammonia, , only a few examples of multimetallic uranium nitrides were so far prepared from dinitrogen cleavage (clusters A–D in Figure ) ,,,, and only in one case intermediates containing less reduced N 2 species could be isolated …”

f-Element heavy pnictogen chemistry

“…amides, imides, and nitrides, but this is not the case for the heavier congeners phosphorus, arsenic, antimony, and bismuth. 18–20 To illustrate the point, a search of the Cambridge Structural Database (CSD, 10th August 2023††Shortly after the census date of this review, reports of a yttrium-bismolyl complex and a yttrium-bismuth cluster were published by Demir and co-workers, and an account of rare-earth phosphinidene complexes was published by Chen and co-workers. See ref.…”

Actinide Triamidoamine (TrenR) Chemistry: Uranium and Thorium Derivatives Supported by a Diphenyl‐tert‐Butyl‐Silyl‐Tren Ligand

“…Given our prior work on uranium-nitrides, [6,9,14,15,34,47] attempts to isolate thorium-nitrides, [6,48] and the wider utility of actinideazides, [66] we examined the synthesis of azide derivatives of 1An. Accordingly, 1Th and 1U were separately treated with excess sodium azide, Scheme 1.…”