Themed collection Most popular 2022 main group, inorganic and organometallic chemistry articles

In this Perspective we compare the ability of transition metals and p-block Lewis acids to activate electrophilically hydrosilanes and hydroboranes. The mechanistic similarities and dissimilarities in different catalytic transformations are analyzed.

Air and water stable germacarbonyl compounds are reported. Thio- 12 and selenogermaamide 13 react with CuX at ambient conditions to afford Cu(I) complexes. Selective binding of 12 and 13 with CuCl and CuBr in a mixture of CuX is seen (X = Cl, Br, I).

From fac to mer and back: a clean, fast and simple procedure for the transformation of fac-Ir(C^N)₃ complexes into the thermodynamically less stable mer isomers is described. The process enables the interconversion of luminophores with distinct photophysical properties.

Redox-active ruthenium complexes supported by hemilabile κ²-N,S-chelated ruthenacycles undergo unusual dual site B–H bond activation through metal–ligand cooperation with free and bulky boranes.

Bis-NHC adducts of the type (NHC)₂·B₂(OR)₄ are sources of boryl radicals of the type NHC–BR₂˙, which are formed by homolytic B–B bond cleavage.

Combinations of ligands were used to tune UNU complexes yielding a U(III)/U(III) nitride, which activates N₂. Parallel N₂ reduction pathways were identified, leading to the first example of N₂ cleavage by U without external alkali reducing agents.

A pair of trigonal imido iron complexes ([Fe(NMes)L₂]^0,−) in two oxidation states is reported. The anionic complex K{crypt.222}[Fe(NMes)L₂] is best described as an iron(II) imide.

Elucidating the role of specific vibrational modes in spin lattice relaxation is a key step to designing room temperature qubits. We executed an experimental and theoretical study on a series of Cu²⁺ qubits to increase their operating temperature.

A revised bonding model for diarylhalonium salts, that involves partial s-orbital contribution, provides new insight into periodic trends in structure and reactivity.

Systems-based elucidation of the polyoxovanadate speciation reveals that heterogroup substitution can transform spherical kegginoids into tubular architectures in a programmable manner.

Geometrically constrained, square pyramidal phosphoranide was synthesized, and its reactivity study showed that it is both a nucleophile and reductant.

A robust dysprosium(III) single molecule magnet with large uniaxial magnetic anisotropy induces pseudocontact shifts at almost doubled distance compared to standard shift agents.

Attempts to form a base-stabilised arylalumylene by reducing an NHC-coordinated diiodoterphenylalane led to a masked dialumene. Reactivity studies showed it decouples to initially aimed arylalumylene, which easily deconstructs less reactive arenes.

A series of tetracoordinate boron-doped polycyclic aromatic hydrocarbons have been synthesized under mild conditions, featuring delayed fluorescence and aggregation-induced emission.

Disproportionation of Cpd II models depends on the electron-richness of the porphyrin ligand; Cpd II with an electron-deficient ligand is difficult to disproportionate, whereas Cpd II with an electron-rich ligand readily disproportionates to form Cpd I as a true oxidant.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.

We disclose the actual octanuclear nature of the major compound from reacting Ni(COD)₂ and PhLi, assigned for more than four decades as ‘Li₃NiPh₃(solv)₃’. We provide a thorough bonding analysis and discuss its potential implications in catalysis.

Metallothioneins (MTs) are a ubiquitous class of small metal-binding proteins involved in metal homeostasis and detoxification.

By using a lead-free AgBi-based scheme, we successfully synthesized a two-dimensional double perovskite ferroelastic (DPA)₄AgBiBr₈ with high T_c of 375 K and a narrow band gap of 2.44 eV, where DPA is 2,2-dimethylpropan-1-aminium.

Aluminyls and carbenes as coordination ligands, although sharing similar electronic properties, reveal fundamental differences in their tunability, bonding to gold and reactivity of their complexes with carbon dioxide.

A novel 2-oxo-imidazole-4-carboxylate (Im^OC) nucleobase, which can be easily derived from a commercially available uridine analogue, was found to form stable Cu^II- and Hg^II-mediated base pairs in DNA duplexes.

A new class of heterotrimetallic COT-based self-assemblies accommodates metals from groups I–III in three different oxidation states and enables tuning of electronic and magnetic properties.

The switching behaviour of spin crossover cocrystals can be modified through changing the coformer and thus co-crystallisation presents a rapid, facile and highly modular tool for the discovery of new switchable materials.

Chlorine K-edge XANES of An(IV) hexachlorides, calculated with multiconfiguration wavefunction theory, is interpreted in terms of similar metal–ligand covalency along the An = Th–Pu series.

A versatile modular approach has been developed for incorporating different metal-oxo nanoclusters with characteristic structures into a single hybrid molecule by covalently linking them with polyol ligands.

New Ru(II) complexes exhibit selective ligand dissociation driven by an excited state trans-type influence. The complexes are not toxic to triple-negative breast cancer cells in the dark, but induce cell death upon irradiation with visible light.

The PNNP expanded pincer ligand can bind two iron centers in close proximity and display heterolytic and homolytic metal–ligand cooperativity.

In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers.

Herein, we exploit site-directed Cu(II)-labeling to measure the DNA conformations in each step of the transcription cycle of the Copper Efflux Regulator (CueR), in order to establish how transcription is activated and terminated.

A series of fully fused boron-doped polycyclic aromatic hydrocarbons is synthesized. Self-assembly of an amphiphilic derivative can be controlled by addition of a Lewis base or an acid in aqueous media.