Themed collection Most popular 2021 main group, inorganic and organometallic chemistry articles, 2021

HNO (nitroxyl, azanone), joined the ‘biologically relevant reactive nitrogen species’ family in the 2000s.

Exporting cooperative effects in main group heterobimetallic reagents to catalytic regimes, this Perspective showcases key advances in their applications for hydroelementation, cyclisation, C–C bond formation and polymerization processes.

Recent development in catalytic application of transition metal complexes having an M–E bond (E = main group metal or metalloid element), which is stabilized by a multidentate ligand, is summarized.

The application of ylide substituents as strong donor ligands for the stabilization of reactive main group compounds with unusual properties and reactivities is discussed.

The first direct synthesis of PhMe₂SiZnI and Me₃SiZnI reagents from silyl iodides is described. They can be obtained as solids and stored at 4 °C for extended periods. The versatility of solid Me₃SiZnI is demonstrated in a variety of reactions.

Copper–ethylene and carbonyl complexes of the newly developed [Ph₂B(3-(SF₅)Pz)₂]⁻ enable the study of ligand steric and electronic effects caused by the –SF₅ group (dubbed “super CF₃”), and a comparison to the –CF₃ bearing analogs.

A change in the sign of the ground state electron spin polarization (ESP) is reported in complexes where an organic radical (nitronylnitroxide, NN) is covalently attached to a donor–acceptor chromophore via two different meta-phenylene bridges.

The differential reactivity of copper, silver and gold aluminyl compounds towards CO₂ and other heteroallenes are probed by experimental and quantum chemical methods.

Vanadium is an abundant and cheap metal but near-infrared luminescent vanadium complexes are extremely rare with largely unexplored photophysics and photochemistry. We delineate the photodynamics of VCl₃(ddpd) to infer novel design strategies.

The ultrafast triplet-to-singlet mechanism, responsible for the photoluminescence of the open-shell V^IIICl₃(ddpd) complex – based on Earth-abundant vanadium – is unraveled using non-adiabatic dynamics in full dimensionality.

An organic–inorganic hybrid perovskite Trimethylchloromethylammonium chromium(II) chloride (TMCM–CrCl₃) can simultaneously show excellent ferroelectricity and antiferromagnetism, which is the first experimentally confirmed Cr²⁺-based multiferroic material.

We report a series of non-toxic cobalt(III) complexes which inhibit Aβ peptide aggregation in vitro; these complexes can be safely delivered across the blood–brain barrier in mice using focused ultrasound.

New Os(II) half-sandwich complexes bearing a pendant alcohol prompt reversible tether-ring formation upon aquation, protecting Os against deactivation. Excitingly, these complexes mediate hydrogenation of pyruvate to lactate inside cancer cells.

A novel 2D halide perovskite with stoichiometric quantities of Cu⁺, Cu²⁺, and In³⁺ in the inorganic slabs shows emergent properties not seen in Cu^II or Cu^I–In^III perovskites, including enhanced visible-light absorption and electronic conductivity.

Highly-symmetrical, thorium and uranium octakis-carbene ‘sandwich’ complexes have been prepared by ‘sandwiching’ the An(IV) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms.

The hemilabile Ad₂P(o-C₆H₄)NMe₂ ligand promotes fast, quantitative and irreversible oxidative addition of alkynyl and vinyl iodides to gold.

Installation of oversized functions within a metal–organic cage may “burst” or even transform the molecular cage itself.

The direct C–H amidation of metallapentalyne has been achieved under mild conditions in which key 1,5-bromoamidated intermediates was determined.

Chelating single-centre ambiphile ligands based upon low-coordinate, acyclic germylenes have been developed, remaining highly Lewis acidic even when bound to Ni⁰, remarkably allowing for the reversible metathesis of the N–H bonds in ammonia at Ge^II.

Frustration at carbon! Herein, we present a frustrated Lewis pair system derived from a water stable carbon-based Lewis acid, trioxatriangulene (TOTA⁺), and a variety of Lewis bases, which successfully promotes bond cleavage and molecule fixation.

One molecule, two response mechanisms: a pair of newly-designed cyclic trinuclear Cu(I) complex crystalline polymorphs are engineered, which show excellent luminescent piezochromism and pressure-induced phosphorescence enhancement, respectively.

Strong bis-cyclometalated iridium photoreductants, in combination with a single sacrificial reductant, enable visible-light-promoted reductive activation of a variety of challenging substrates under simple and general reaction conditions.

Framework-associated aluminum is demonstrated to facilitate a reversible switch between Lewis and Brønsted acidity in zeolites with the Lewis acid sites preferentially populating the side-pockets in the case of mordenite.

The therapeutic alpha-emitter ²²³Ra can be stably complexed in vivo, creating opportunities for the development of targeted radiopharmaceutical agents with this radionuclide.

Combined experimental and theoretical Ru 2p4d resonant inelastic X-ray scattering study probes the chemical bonding and the valence excited states of solvated Ru complexes.

The direct chemical reduction of CAACCO2 adducts by alkali metals to yield multinuclear clusters is reported. The mono- and dianions of CO₂ have been studied for decades and are fundamentally important oxycarbanions and critical species in CO₂ fixation chemistry.

Complexes of a highly Lewis acidic Mg cation and the full series of Ph–X (X = F, Cl, Br, I) have been structurally characterized. The Mg⋯X–Ph angle decreases with halogen size on account of the growing halogen σ-hole.

A “protecting group strategy” for unstable lacunary polyoxomolybdates enabled successful synthesis of two types of tetranuclear manganese clusters.

A di(o-tolyl)borylgold complex added to CO/N double bond to form Au–C and B–O/N bonds. DFT calculations revealed a two-step mechanism consisting of the coordination of O/N atom to B atom followed by nucleophilic migration of Au atom.

[Dy^III(SCN)₃(depma)₂(4-hpy)₂] (1) shows reversible thermo-induced phase transition associated with thermochromism and dielectric anomaly and photo-induced dimerization with synergistic switching of luminescence, magnetic and dielectric properties.

Ho^III complexes bearing organic luminophores and inorganic metalloligands are an effective tool for achieving the unique conjunction of single-molecule magnetism and thermometric luminescence re-absorption phenomenon.

Synthesis of a triangular [Pd₂Ru]⁺ complex with delocalized metal–metal bonding between non-adjacent elements of the periodic table, double aromaticity and overlap of d-AOs with different angular momentum.