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The parent diphosphene molecule is of fundamental interest, but its reactive nature renders it challenging to isolate, and current metal-stabilized derivatives are limited to complexes of p-/d-metals. Here, the authors introduce f-element diphosphene complexes, adding to f-element diazenes that were first reported over thirty years ago.

Although uranium-nitrogen multiple bonding is well developed, there are far fewer uranium-phosphorus and -arsenic multiple bonds, and none for antimony, even in spectroscopic scenarios. Here, the authors report syntheses of uranium-stibido, -stibinidiide, -distibene, and -stibinidene derivatives containing single, double, and pseudo-triple bond interactions.

Owing to the propensity for uranium(III) compounds to undergo disproportionation, uranium-element multiple bonds involving uranium(III) oxidation states remain rare. Here the authors report hexauranium-methanediide rings that formally contain uranium(III)- and uranium(IV)-methanediides supported by alternating halide and arene bridges.

Superatoms are metal clusters that collectively behave like an atom, but they usually require metal–metal bonding and thus they are based on main group or transition metals. Now it has been shown that trithorium nanoclusters with delocalized three-centre-one-electron thorium–thorium bonding exhibit exalted diamagnetism. This unveils actinide superatoms that exhibit open-shell jellium aromaticity.

Despite the burgeoning field of uranium-ligand multiple bond chemistry, analogous thorium compounds remain scarce. Here, the authors synthesize and characterize a series of thorium complexes with multiple bonds to phosphorus, and probe their 5f versus 6d orbital bonding character.

Actinide electronic structure determination is fundamentally challenging. Here, the authors assemble a family of uranium(V)-nitrides and quantify the electronic structure of the molecules, defining the relative importance of spin orbit coupling and crystal field interactions.

Advances in actinide chemistry have led to the isolation of a range of uranium–ligand multiple bonds, but analogous thorium complexes are rare. Here, the authors prepare thorium–arsenic complexes that are stabilized by bulky triamidoamine ligands and exhibit ThAsH2, ThAs(H)K, ThAs(H)Th and ThAsTh linkages.

In actinide chemistry, a longstanding bonding model describes metal-ligand binding using 6d-orbitals, with the 5f-orbitals remaining non-bonding. Here the authors explore the inverse-trans-influence — a case where the model breaks down — finding that the f-orbitals play a crucial role in dictating a trans-ligand-directed geometry.

Actinide–metal multiple bonds are relatively rare, with isolable examples under normal experimental conditions typically restricted to complexes containing a polar covalent σ bond supplemented by up to two dative π bonds. Now complexes featuring polar covalent double and triple bonds between thorium and antimony have been synthesized.

Despite their importance as mechanistic models for Haber Bosch ammonia synthesis from N₂ and H₂, high oxidation state terminal metal-nitrides are notoriously unreactive towards H₂. Here, the authors report hydrogenolysis of a uranium(V)-nitride, which can occur directly or by Frustrated Lewis Pair chemistry with a borane ancillary.

Despite the burgeoning nature of uranium–ligand multiple bonding, analogous thorium complexes remain incredibly rare. Here the authors report evidence for a transient thorium–nitride species, which, together with data on parent imido derivatives, suggests that the pushing-from-below phenomenon may be more widespread than previously thought.

Neptunium was the first actinide to be artificially synthesized, yet its chemistry has remained relatively unexplored. Most neptunium chemistry involves the neptunyl di(oxo) motif, and transuranic compounds with only one metal–ligand multiple bond are generally rare. Now, a stable complex of neptunium in the +5 oxidation state has been isolated that features a single terminal Np–O multiple bond.

Disproportion of uranium(IV) is rare, as it is usually the stable product of uranium(III) or (V) disproportionation. Here, the authors report uranium(IV) disproportionation to uranium(III) and (V) revealing ligand and solvent control over a key thermodynamic property of uranium

A crystalline cluster exhibits thorium–thorium bonding, adding to our knowledge of actinide–actinide bonding.

In coordination and organometallic chemistry, back-bonding between an electron-rich, typically mid- or low-oxidation-state d-block metal centre and a ligand with accepting π* orbitals is widespread. Now, such an interaction has been observed between unlikely partners—high-oxidation-state uranium(v) 5f¹ ion and the poor π-acceptor ligand dinitrogen—in a U(v)–bis(imido)–N₂ complex stabilized by a lithium counterion.

The reactivity of f-block complexes is primarily defined by single-electron oxidations and σ-bond metathesis. Here, Liddle and co-workers provide evidence that a uranium complex can undergo reversible oxidative addition and reductive elimination, demonstrating transition metal-like reactivity within f-block chemistry.