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Notwithstanding their success as strongly σ-donating and π-accepting ligands, to date no chelating bis[cyclic (alkyl)(amino)carbenes] have been reported. Here the authors describe a chelating, C₂-symmetric bis[cyclic (alkyl)(amino)carbene] ligand, as well as its pseudotetrahedral complexes with iron, cobalt, nickel, and zinc dihalides.

Chemical reduction of alkali cations to their metals is extremely challenging. Here, the authors synthesized a series of redox-active borate anions stabilized by bipyridine ligands which can reduce lithium ions generating elemental lithium metal and borate radicals.

Bis(N-heterocyclic carbene)-borylene complexes are capable of capturing and functionalizing CO₂, but stable single-site-boron-carbon dioxide adducts are rarely reported. Here, the authors report the synthesis of a stable borylene-CO₂ complex as well as the functionalization of the captured CO₂.

Coordination-induced bond weakening (CIBW) by redox-active metals is used to weaken bonds in water and ammonia to facilitate proton-coupled electron transfer but achieving CIBW using aluminium as abundant metal is challenging. Here, the authors report a system that uses aluminum with a redox non-innocent ligand to achieve CIBW of O-H and N-H bonds.

A previous investigation of the anti-aromatic dianion of [18]annulene concluded that it consists of a mixture of two isomers. Now it has been shown that this dianion exists as a single isomer, with a different geometry from neutral [18]annulene, and that it can be reduced further to an aromatic tetraanion.

The in situ generation of reactive (di)gallenes from a gallium–fluorobenzene complex and commercial chiral and achiral bisphosphine ligands is presented. The Ga(I) complex cations can undergo reversible cycloadditions to 1-alkenes and bond insertions into H–Si and H–B bonds.

Ion exchange is a powerful method to access metastable materials for energy storage, but identifying lithium and sodium interchange in layered oxides remains challenging. Using such model materials, vacancy level and corresponding lithium preference are shown to be crucial for ion exchange pathway accessibility.

Hong et al. report 2D perovskite lateral homojunction consists of ordered and disordered phases, achieved by organic cation doping induced phase pinning, built upon which they develop tuneable optical properties under external stimuli and directional exciton diffusion in the homojunctions.

Circularly polarised luminescence (CPL) is essential for asymmetric synthetic photochemistry. Here, the authors integrate white quantum dots with chiral nematic liquid crystal or liquid crystal polymer to achieve single-emitted tuneable full-colour or white CPL for enantioselective polymerization.

The development of new methodologies to convert plastics into fuels without relying on noble metal-based catalysts is desirable. Now it is shown that a layered self-pillared zeolite enables the conversion of polyethylene to gasoline with a selectivity of 99% and yields of >80% without the need to use external hydrogen.

Icosahedral carboranes have long been considered to be aromatic but the extent of conjugation between these clusters and their substituents is still being debated. Here the authors demonstrate carboranes as conjugated bridges in optical functional chromophores.

This study introduces a Eu(II) single molecule magnet that exhibits slow magnetic relaxation at low temperatures. These results highlight the importance of the lanthanide ion’s crystal field in unlocking the magnet-like properties of Eu(II).

Here the authors demonstate that counter to expectation provided by the relevant standard reduction potentials, a chloroberyllate, [{SiNDipp}BeClLi]2, reacts with the group 1 elements (M = Na, K, Rb, Cs) to provide the respective heavier alkali metal analogues, [{SiNDipp}BeClM]2.

The structure of GeO₂ melt has been debated for decades due to several unexplained bands present in the GeO2 melt Raman spectra. Here authors present a promising way to analyse melt structures from Raman spectra and they demonstrate threefold coordinated germanium is formed in the GeO₂ melt.

Chiral luminescent materials are of increasing interest in various applications, but achieving a desirable balance of properties can be challenging. Here, the authors report the development of Eu-based complexes with chiral luminescence and aggregation induced emission.

Understanding and exploiting the redox properties of uranium is of great importance but stabilizing both low and high valent uranium ions in a preserved ligand environment remains challenging. Here, the authors report the synthesis and characterisation of a series of uranium(II–VI) complexes supported by a tripodal tris(amido)arene ligand.

Controlled atomic delivery is a desirable synthetic process. Here a germanium-substituted phenyl anion is shown to act as a germanium atom transfer reagent and demonstrated by the preparation of well-defined molecular germanium species.

The authors demonstrate that carbides with infinite chains of fused [C6] and [C5] rings are synthesized at deep planetary pressures and temperatures. Hydrolysis of these carbides may lead to polycyclic aromatic hydrocarbons in the Universe.

Amidst vanadium’s growing demand and environmental concerns in mining, the researchers, using naphthalimidedioxime, crafted a breakthrough method for eco-friendly recovery. Their acid-stable agent and non-toxic complexes offer a promising solution for large-scale vanadium recovery from diverse sources.

Diatomic C₂ is an elusive species that has only been indirectly observed in the gas phase. It had previously been stabilized in the condensed phase using two ligands, but now a monoligated L→C₂ complex has been prepared with a bulky phosphine ligand (L) bearing two imidazolidin-2-iminato groups. Reactivity studies and theoretical quantum chemical analysis point to the C₂ moiety having a dicarbene character.

A method is developed for the directional optimization of multiple properties without prior knowledge on their nature. Using a large ligand dataset, diverse metal complexes are found along the Pareto front of vast chemical spaces.

A series of molecular rare-earth telluride clusters incorporating a three-centre, four-electron, tri-tellurido ligand (Te₃⁴⁻) are reported. These atomically precise clusters, possessing ultralow band gaps comparable to those of monocrystalline silicon and gallium arsenide, are potentially applicable as quantum materials and for optoelectronic applications.

Although the light-driven generation of hydrogen from water is a promising approach to renewable fuels, the H–H bond formation step represents a persistent mechanistic question. Now light-harvesting molecular catalysts have been shown to self-assemble into nanoscale aggregates that feature improved efficiency for photoelectrochemical H₂ evolution.

A two-coordinate monovalent gold complex that features a highly polarized aluminium–gold covalent bond, Al^δ+–Au^δ−, has been synthesized using a very strongly electron-donating aluminyl ligand. In solution, the complex reacts as a nucleophilic source of gold towards heteroallenes such as carbodiimides and CO₂.

Metal–ligand cooperative catalysis involves both the metal and the ligand moieties present in a complex interacting with substrates. Cooperative catalysis is central to the mechanisms of hydrogenases, lactate racemase and alcohol dehydrogenase. This Perspective describes these enzymes, as well as the small-molecule mimics inspired by these elaborate natural catalysts.

Pre-intercalation with alkali-metal ions is attractive for accessing higher reversible capacity and improved rate performance in Li-ion batteries. Topochemical single-crystal transformations in a tunnel-structured positive electrode are used to clarify the effect of pre-intercalation in modifying the host lattice and altering diffusion pathways.

Iron atoms in a synthetic metal–sulfur cluster can capture nitrogen and catalyse its silylation, demonstrating successful nitrogen reduction by iron atoms in a sulfur-rich environment.

The design, synthesis and characterization of a series of circular sandwich compounds, cyclocenes, is described, and these cyclic sandwich compounds are expected to lead to further innovations in new functional organometallic materials.

The authors discover high-pressure Sc₂N₆, Sc₂N₈, and ScN₅ polynitrides, synthesized at high pressure and temperature conditions, featuring a unique nitrogen catenation and previously unknown N₆⁶⁻ anions, N₈⁶⁻ anions and anionic corrugated 2D-polynitrogen layers.

Carbyne anions are under explored and poorly understood, owing to their isolation being unknown. Now, the synthesis and isolation of copper phosphinocarbyne anion complexes are reported. Displaying the reactivity of a carbyne anion, these complexes provide access to singlet carbenes, alkenes and ethenimines.

Coordination of benzene by a tungsten complex can minimize the formation of oligomeric aromatic products in Friedel-Crafts Arylation. Here the authors show that coordinating benzene to tungsten through two carbons (dihapto-coordination) enables a rarely observed double protonation of the bound benzene, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.

Lithium cobalt oxide is widely studied for electrocatalytic applications. Here, the authors develop a technique for delithiating the material in organic electrolyte, and demonstrate that the oxygen evolution catalytic activity is significantly improved after the treatment.

Biomass-derived monomers are a renewable resource for the production of polymers. Robertet al. develop an auto-tandem catalytic transformation for the synthesis of aliphatic polyesters—'activated' monomers are prepared from dicarboxylic acids, which can be copolymerized with epoxides.

Activation of C–C bonds is a powerful method for directly functionalizing organic molecules, but is still a challenging task. Here, the authors show that N-heterocyclic carbenes can activate the C–C bonds in cyclic ketones, allowing the enantioselective formation of lactams.

Zinc(I) bimetallic clusters have previously been reported, but they are not stable in air. Here, the authors synthesize octametallic Zinc(I) clusters with multi-centred zinc–zinc bonds and extensive electron delocalization over the cluster, resulting in cubic aromaticity and enhanced stability.

Boron is known to form a wide variety of molecular structures. Here, the authors observe the highly symmetric cobalt-centered boron drum-like structure of CoB₁₆⁻, characterized by photoelectron spectroscopy and ab initio calculations, in which the cobalt atom is sixteen-coordinate.

Fundamental understanding of gold–carbon bonding in homogeneous catalysts is vital for improved catalyst design, although spectroscopic information is limited. Here, the authors probe the bonding in gold–alkyne complexes using a combination of photoelectron spectroscopy and ab initiocalculations.

σ-Complexes of transition metals are key intermediates in metal-mediated bond activation, but have traditionally been isolable only when chelating or when one of the participating atoms is hydrogen. Here, a complex is isolated with an unsupported borirene ligand bound not through the unsaturated C=C bond, but exclusively via a B–C single bond.

Converting low-cost inorganic chemicals into value-added organic chemicals is a longstanding goal in chemistry. Here the authors describe a silver-catalysed chemoselective carbene N−H insertion reaction, providing access to primary amines from aqueous ammonia and diazo compounds.

Cation–anion exchange between dimers to prepare mixed aggregates with Mg–Ae (alkaline earth) bonding (Ae = Mg, Ca, Sr, Ba) is reported. Considerable electron transfer from the (BDI)Mgˉ anion (BDI, β-diketiminate) to Ae and Na atoms is observed, and the reactivity of these electron-rich complexes with Na–Mg–Ae bonding is discussed.

Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Here, the authors report the synthesis of a silylene-stabilized ditin(0) complex by reduction of a silylene-supported dibromostannylene and its conversion to methylditin cation and distannavinylidene

Oxygen redox cathodes deliver higher energy densities than those based on transition metal redox but commonly exhibit voltage fade on extended cycling. The loss of O-redox capacity and voltage fade is shown to arise from a reduction in O²⁻/O₂ redox process reversibility and O₂ loss.

Owing to the electropositive character of aluminium it is difficult to prepare Al anions; the few that exist are supported by nitrogen ligands. Now, a dialkyl-alumanyl anion has been synthesized that features a polar Al–K bond. This anion reacts as a very strong base that deprotonates benzene, and undergoes nucleophilic substitution reactions.

Beryllium in inorganic compounds is usually coordinated to four oxygen atoms, but higher coordination numbers have been predicted. Here the authors observe a pressure induced stepwise transition in CaBe₂P₂O₈ where Be coordination changes to trigonal-bipyramidal and octahedral, implying that d orbitals are not mandatory for high coordination.

The authors manipulate two categories of cathodes for sodium-ion batteries for a rational design that combines high energy density with high power density and long cycling life.

Molecular ferroic materials receive considerable interest in view of field-induced switchable polar/magnetic orders. Here, the authors exploit metal-free antiferroelectrics in molecular solid solutions to assemble high-performance ferroic materials.

It is difficult to investigate the chemical properties of superheavy elements, which are only available an atom at a time and rapidly decay. A co-precipitation method with samarium has now been developed that suggests rutherfordium would form hydroxide precipitates—but not ammine ones—if it were possible to perform these experiments on macroscopic quantities.

Many alkyl fluorides are readily available, but the synthetic applications trail behind the widely accepted utility of other halides. Here, the authors report a practical Csp3-F bond functionalization method that expands the currently restricted synthetic space of unactivated C(sp3)-F bonds, but also uses benzylic, propargylic and acyl fluorides.

Nitrogenase—whose cofactor consists of a metal–sulfur cluster—catalyzes the production of NH₃ from N₂, but designing metal–sulfur complexes capable of promoting this conversion remains challenging. Here, the authors report on the activation of N₂ by a metal–sulfur cluster containing [Mo₃S₄Ti] cubes, demonstrating NH₃ and N₂H₄ production.

Vinylidene, (H₂C=C), is a short-lived structural isomer of acetylene. By employing bulky and strongly electron-donating boryl co-ligands, the synthesis of an analogous group 14 vinylidene compound is reported. The digermavinylidene, {(HCDippN)₂B}₂GeGe, (where Dipp = 2,6-ⁱPr₂C₆H₃), is synthesized via oxidation of the corresponding symmetrical Ge⁰ compound K₂[(boryl)GeGe(boryl)].