Nature Reviews Chemistry, Published online: 27 November 2025; doi:10.1038/s41570-025-00781-9Unsymmetric coordination environments are prevalent in metalloenzymes. By contrast, most synthetic homogeneous catalysts rely on symmetric ligand frameworks. This Review highlights biological unsymmetric bimetallic centres along with their roles in catalysis and illustrates how intentionally incorporated unsymmetry in synthetic systems mimics nature’s strategies for achieving cooperative and complementary reactivity.

The reactivity of the kinetically stabilized stannylene (MesTer)2Sn (1) (MesTer = –C6H3-2,6-(2,4,6-Me3-C6H2)2) toward N2O is revisited, yielding the terminal tin(IV) hydroxide 2 via formal intramolecular C(sp3)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)2 (3) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)2Sn (4). Compound 4 can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (6). Both 4 and 6 serve as suitable precursors for the synthesis of the heteroleptic s-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe3)2} (5).

Scandium and chromium compounds team up to convert iconic molecule into linear product at room temperature

Nearly all photochemical transformations known to date follow Kasha’s rule, implying that reactions occur only from the lowest electronically excited state of a given spin multiplicity due to the fast...

Nature Reviews Chemistry, Published online: 30 May 2025; doi:10.1038/s41570-025-00718-2X-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.

Class I and II benzoyl-coenzyme A reductases offer a mild biological alternative to the alkali metal- and ammonia-dependent Birch reduction, a classical synthetic method for achieving dihydro addition...

Luminescence and photochemistry involve electronically excited states that are inherently unstable and therefore spontaneously decay to electronic ground states, in most cases by nonradiative energy release that generates heat. This energy dissipation can occur on a time scale of 100 fs (∼10–13 s) and usually needs to be slowed down to at least the nanosecond (∼10–9 s) time scale for luminescence and intermolecular photochemistry to occur. This is a challenging task with many different factors to consider. An alternative emerging strategy is to target dissociative excited states that lead to metal–ligand bond homolysis on the subnanosecond time scale to access synthetically useful radicals. Based on a thorough review at the most recent advances in the field, this article aims to provide a concise guide to obtaining luminescent and photochemically useful coordination compounds with d-block elements. We hope to encourage “photo-motivated” chemists who have been reluctant to apply their synthetic and other knowledge to photophysics and photochemistry, and we intend to stimulate new approaches to the synthetic control of excited state behavior.

Following the building principles of crown ethers for cation encapsulation, inverse crowns are rings of metals that bind anions. Now a redox-active inverse crown ether featuring Na+ cations and Mg0 ha...

Guest editor Paula Hammond, MIT drug delivery pioneer, describes her vision for this special issue of C&EN celebrating Black Trailblazers in chemistry and chemical engineering

All-metal aromatic monocycles are still rare, in contrast to their ubiquitous organic counterparts, because metal atoms tend to form clusters with multiply bonded atoms instead. Now a planar aromatic ...