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Catalytic asymmetric synthesis of stable, acyclic N-stereogenic amines by the addition of enol silanes to nitronium ions that ion pair to a confined chiral anion is described.

Mononuclear complexes of certain lanthanide ions are known to have large magnetization reversal barriers caused by strong spin–orbit coupling. Now, careful tuning of the ligand field of a transition metal complex has engendered a comparable spin-reversal barrier — and in turn magnetic blocking at 4.5 K.

Heavier analogues of unsaturated organic molecules are of interest because of their bonding situation and their potential use in synthesis. Now, a Bi(I)-based allyl cation, which can be seen as a heavy congener of all-carbon π-allyl cations, has been reported. This complex serves as a synthon for Bi(I) transfer, enabling access to low-valent organobismuth compounds.

Puzzarini and colleagues explore the computational characterization of medium-sized molecular systems using different spectroscopic techniques. The Primer provides essential information about the characteristics, accuracy and limitations of current computational approaches used for modelling spectroscopic phenomena with a focus on estimating error bars, limitations and coupling interpretability to accuracy.

The catalytic mechanism of [Fe]-hydrogenases is not well understood. Now a signal-enhanced nuclear magnetic resonance method based on parahydrogen is introduced to study [Fe]-hydrogenase under turnover conditions in situ, revealing intermediates of the catalytic cycle.

An approach for the direct electrophilic C–H fluorination of arenes is reported, using a palladium catalyst and mild fluorinating reagents.

The synthesis, structure and reactivity of room-temperature-stable [Cp(C₆F₅)₅]⁺[Sb₃F₁₆]⁻ is presented. Coordination of the cyclopentadienyl cation by [Sb₃F₁₆]⁻ or C₆F₆ stabilizes the antiaromatic singlet state in the solid state. Calculated hydride and fluoride ion affinities of the [Cp(C₆F₅)₅]⁺ cation are higher than those of the tritylium cation [C(C₆F₅)₃]⁺.

X-ray spectroscopy offers element-selective probes of diverse (bio)chemical systems. Close coupling of experiment with ab initio calculations unveils the rich electronic structural information available and facilitates practical, chemical interpretation of spectra, as discussed in this Review.

Understanding the catalytic mechanism of redox-active hydrogenases is a key to efficient hydrogen production and consumption. Here, the authors use nuclear resonance vibrational spectroscopy to study [NiFe]-hydrogenase, and observe a bridging hydride structure in an EPR silent intermediate.

Transition metal complexes that display slow magnetic relaxation show promise for information storage, but our mechanistic understanding of the magnetic relaxation of such compounds remains limited. Here, the authors spectroscopically and computationally characterize the strength of spin–phonon couplings, which play an important role in the relaxation process.

Bistable single-molecule magnets potentially allow information storage at extremely high densities. Here, the authors study an air- and moisture-stable mononuclear tetrahedral cobalt(II) complex, elucidating the origin of its pronounced magnetic bistability.

FeS clusters are a universal motif in organisms and are central to many processes, including nitrogen fixation and respiration. By carrying out the first many-electron calculation of the [2Fe-2S] and [4Fe-4S] clusters, they are shown to have an unusual set of closely packed energy levels, which are key to understanding their reactivity.

The four-coordinate iron sites of typical iron–sulfur clusters rarely react with small molecules, implicating three-coordinate iron in many catalytic cycles. Now, a [4Fe-3S] cluster featuring three-coordinate iron sulfide that resembles the proposed substrate binding site has been synthesized. This cluster shows biomimetic reactivity with a low-spin electronic configuration.

The integration of quantum chemistry and molecular dynamics programs coupled with a graphical user interface provides a streamlined tool for powerful simulations of biomolecular reaction mechanisms.