Chemical reaction databases have become core scientific infrastructure. Most prominent datasets focus on or- ganic reactions, or only include reactants and product rather than full reaction pathways, leaving organometallic chemistry particularly underserved despite its centrality to homogeneous catalysis. This gap limits the develop- ment of machine learning models for organometallic reactions and limits applications in mechanism discovery, selectivity prediction, and catalyst design. This work introduces an open, reaction-centric resource derived from XXX SI across 50+ journals from seven publishers through 2025 using the Gold-DIGR (Gold-Data Integration for Generalized Reactions) workflow. Reported organometallic reactions are aggregated and reaction properties extracted or recalculated, including reactant, product, and transition-state geometries, intrinsic reaction coor- dinate (IRC) traces, reaction classes, and ligand/metal descriptors (coordination, valence-electron counts, bond orders). Bond–electron matrices enable electron-flow analyses along reaction coordinates, visualized as Sankey diagrams connecting local electron rearrangements to class-level patterns. The resulting corpus spans canoni- cal classes—oxidative addition, reductive elimination, migratory insertion, β-hydride elimination, C–H activation, transmetalation, and σ-bond metathesis—enabling quantitative mechanistic analyses at scale. As a demonstration of the meta-analyses enabled by this broad-based data generation, the relationship between bond-breaking/forming events and the transition states are studied to investigate concerted versus sequential scenarios. Class-specific tim- ing asymmetries emerge, with reductive elimination and β-atom elimination events skewed pre-transition-state, oxidative addition and migratory insertion skewed post-transition-state, and transmetallation showing the broad- est dispersion. By releasing both tooling and data, this work provides a foundation for mechanistic benchmarking and data-driven catalyst design.

Altermagnetic materials have recently garnered significant attention due to their combined advantages of spin-splitting characteristics inherent to ferromagnets and the zero-net-moment stability of antiferromagnets. p-electron spintronics materials intrinsically exhibit long-distance spin coherence and long

Photo-active molecular systems play an essential role in modern science and technology, finding applications in solar cells, organic light-emitting diodes (OLEDs), reaction catalysis, photodynamic therapy, and beyond. The rational design of photo-responsive molecules requires understanding of the photophysical and photochemical processes underlying their operation. This understanding can be gained via the first-principles quantum-mechanical (QM) calculations which, however, turn out prohibitively expensive for high-throughput investigations. To break through this limitation, here we introduce OMNI-P2x: the first universal neural network potential for molecular excited and ground electronic states. OMNI-P2x can be used, directly or after fine-tuning, in place of quantum-mechanical methods to perform a wide range of photophysical and photochemical simulations. OMNI-P2x is approaching the accuracy of time-dependent density functional theory (TD-DFT) methods at a fraction of the cost. Remarkably, this universal potential is more accurate and faster than established semiempirical QM methods, marking the watershed moment in theoretical method development for excited-state simulations. Here, we demonstrate its use in UV/Vis absorption spectroscopy, in real-time photodynamical simulations, and in the rational design of the visible-light-absorbing azobenzene systems.

Accurately modeling non-covalent interactions (NCIs) involving charged systems remains an outstanding challenge in Density Functional Theory (DFT), with implications across natural and life sciences, engineering, e.g., in biochemistry, catalysis, and materials science. For these interactions, the interplay between electrostatics, polarization, and dispersion leads to systematic errors of up to tens of kcal/mol in standard dispersion-enhanced DFT methods. We solve this problem by introducing (r2SCAN+MBD)@HF, a DFT method without empirically fitted parameters that combines the r2SCAN functional and many-body dispersion, both evaluated on Hartree-Fock densities. We show that the unique synergy of these three components enables balanced treatment of short- and long-range correlation, which is crucial for accurate description of NCIs involving charged systems. Evaluations on standard benchmarks and a new Metal Ion Protein Clusters dataset introduced here show that (r2SCAN+MBD)@HF significantly improves accuracy for NCIs involving charged systems while maintaining robust performance for neutral systems. Given the ubiquity of such interactions, (r2SCAN+MBD)@HF is broadly applicable from biochemistry and materials science, including for generating high-quality data to train machine-learning force fields.

We report a transition metal-free method for the intermolecular hydroamination of olefins using solvated electrons, generated in situ from granulated lithium under sonication in 2-methyltetrahydrofuran (2-MeTHF). This additive-free protocol enables rapid formation of mixed secondary and tertiary amines under ambient conditions with broad substrate scope and functional group tolerance. Mechanistic studies support an SET and HAT pathway, with lithium amide intermediates acting as both reductants and nucleophiles. The method offers excellent atom economy, sustainability, and synthetic utility, exemplified by the selective synthesis of the racemic version of the pharmaceutical benzphetamine in high yield.

In cross-couplings of dihaloarenes, the step(s) that take place at the end of one catalytic cycle—after reductive elimination—and before the start of the next (before oxidative addition) influence the selectivity for mono- versus difunctionalization. When palladium is supported by a bulky ancillary ligand “L”, a competition exists between a second oxidative addition (leading to difunctionalization) and bimolecular displacement of Pd0 from the monofunctionalized product by a second smaller ligand. Because oxidative addition of aryl bromides is faster than aryl chlorides, more difunctionalization might be expected with dibromoarenes compared to dichloroarenes. However, the opposite has been reported in some Suzuki-Miyaura cross-couplings. Here, we investigate the mechanistic origin of this counterintuitive trend to explain why dibromoarenes can sometimes be less prone to diarylation, despite undergoing faster oxidative addition than their chlorinated analogues. The selectivity outcome is found to be closely tied to solvents: the discrepancy between the expected and actual selectivity with dibromoarenes primarily appears in oxygen-containing solvents of at least moderate polarity (like THF), whereas high selectivity for diarylation can be achieved in most aromatic and chlorinated solvents. The results suggest that, in polar oxygen-containing solvents, bromide anion (formally dissolved KBr, the byproduct of oxidative addition) displaces LPd0 from the mono-cross-coupled product as anionic [BrPd0L]–. Based on product distributions in these solvents, the rate of this process is competitive with the rate of intramolecular oxidative addition en route to the diarylated product. In contrast, the analogous displacement of Pd0 by chloride (the byproduct when using dichloroarenes) appears to be a much slower process, if it occurs at all.

A method for the olefination of aryl aldehydes with unactivated alkenes via cross carbonyl-olefin metathesis (XCOM) is described. Reaction of an aldehyde substrate and a cis-1,2-disubstituted or monosubstituted olefin with the HBF4 salt of 2,3-diazabicyclo[2.2.2]octane results in high-yielding olefination with exclusive trans stereoselectivity. The reaction is shown to accommodate a range of substitution patterns on the aryl aldehyde and a diverse set of functional groups, including protic functionality that would complicate traditional olefination methods. We show that product inhibition arising from the aliphatic aldehyde side product limits catalytic turnover, but that distillative removal of this component renders catalysis feasible.

This work reports a computational-aided design driven approach towards chiral chalcogen-bond donor structures able to accomplish the still unprecedented, highly challenging asymmetric chalcogen-bonding catalysis. Optimisation of the chiral central backbone in rather simple bistriazole-bistelluride-based structures to effect a bidentate binding to Lewis basic substrates was performed, leading to the identification of (R,R)-1,3-diamino cyclohexane moiety as appropriate chiral spacer. While no binding was observed for other chiral central backbones, a moderate affinity to chloride anion as model substrate was recorded for the optimised neutral, bidentate system (Ka ~50-60 M-1 in THF-d8), for which key binding features were further revealed upon computational analysis on the corresponding catalyst-chloride complex. Hence, a chiral induction using chalcogen-bond as main activation was achieved for the first time, reaching enantioselectivities of up to 11:89 e.r. (78% ee) in the chosen test anion-binding benchmark Reissert-type reaction of (iso)quinolines.

Nucleophilic catalysis is a powerful and well-developed tool for the activation and manipulation of carbon-centered electrophiles, yet, routes for its utilization have been limited to a handful of molecular moieties. Herein, we report that dimethylaminopyridine efficiently promotes the nucleophilic substitution reactions of β-chlorinated Michael acceptors with various O-, N-, S- and C-nucleophiles in terms of electronic and steric properties. The reactions proceed via the formation of vinylpyridinium electrophilic species, which can be either generated in situ under catalytic conditions or, more beneficially, isolated and used further in a separate synthetic step. The executed reactions include preparation of relevant pharmaceutical precursors and cascade processes. Furthermore, quantum chemical calculation methods quantified a rate increase of the key substitution step of a catalytic reaction by approximately 10^6 times compared to a non-catalyzed reaction and established an impact of intermolecular noncovalent interactions on the reaction course.

Over the past twenty years, main group chemistry has broadened its horizons to encompass reactivities once thought to be exclusive domains of transition metals. Element-ligand cooperation has emerged as a promising approach for enabling bond activation reactions, yet it remains relatively unexplored for heavier group 15 elements. In this study, we present a novel class of ylide ligands featuring additional amino donor sites, specifically designed to promote bismuth-ligand cooperativity. We successfully isolated a series of well-defined bismuth scorpionate complexes with a dianionic N,Cylide,N ligand, bearing different substituents at the ylide moiety. These variations result in differing degrees of negative charge stabilization, which in turn leads to variable donation of electron density to the central bismuth atom. Halide abstraction to form cationic bismuth complexes enhanced ligand-to-bismuth electron donation, resulting in low Lewis acidities and reduced reactivity. Conversely, deprotonation of the ylide ligand bearing an electron-withdrawing ArF substituent enabled the synthesis and NMR characterization of a rare bismuth yldiide, which underwent a [2+2] addition of carbodiimide across the formal Bi=C double bond, demonstrating the ability of bismuth yldiides to activate bonds through bismuth-ligand cooperativity.

The combination of hypervalent iodine(III) oxidants and ammonia sources has been applied in various oxidative aminative transformations of high synthetic value. Central to these reactions is the proposed in situ generation of a four-electron oxidizing intermediate, commonly referred to as iodonitrene. However, this species’ mechanism of formation, nature, and relevance to N-atom transfer remains uncertain. Furthermore, evidence for its direct implica-tion as the key reactive intermediate remains elusive. Herein, we present an extensive mechanistic study of a re-cently published oxidative aminative cleavage of alkenes, which allowed us to obtain key insights into these under-studied aspects of hypervalent iodine-mediated nitrogen atom insertion. Through in situ 19F nuclear magnetic reso-nance (NMR), initial rate kinetics, linear free energy relationships (LFER), H/D and 12C/13C kinetic isotope effect (KIE) determination, electrospray ionization mass spectrometry (ESI-MS) and density functional theory (DFT) stud-ies, we show that the formation of an N-iodonium-iminoiodinane is rate-determining in this reaction. This species is highly electrophilic and capable of concerted, asynchronous transfer of a [PhI–N]+ unit to double bonds. These find-ings point towards the N-iodonium-iminoiodinane, not an iodonitrene, being the active N-atom transfer agent gen-erated from the combination of hypervalent iodine(III) oxidants and ammonia. This ultimately deepens our under-standing of this commonly used reagent combination and will help to inform the development of methods and rea-gents for oxidative amination reactions using this reactive manifold.

Oxygen-atom transfer (OAT) reactions, such as epoxidation, often use stoichiometric high-energy oxygen donors that present safety hazards, especially on large scale. Electrochemistry provides a means to replace these reagents with water as the O-atom donor. Here, we identify an electron-deficient Mn-porphyrin electrocatalyst that enables efficient OAT to alkenes and pyridines to access epoxides and N-oxides. The scope of the reaction includes terminal and electron-deficient alkenes that often prove challenging with other chemical and electrochemical methods. Direct comparisons with two chemical oxidation methods, (i) stoichiometric meta-chloroperoxybenzoic acid and (ii) the same Mn-porphyrin catalyst with PhI(OAc)2 as the oxidant, highlight the merits of the electrochemical reaction. Prospects for scalable application of the method is demonstrated through oxidation of pharmaceutically relevant alkenes in a stirred tank electrochemical reactor.

A thorough mechanistic investigation into the disulfonimide (DSI)-catalyzed atroposelective iodination of 2-amino-6-arylpyridines with N-iodosuccinimide is described. While initially hypothesized to proceed via Brønsted-acid catalysis through activation of NIS, experimental evidence led us to reconsider the possible function of the DSI catalyst. We now propose a mechanism in which the conjugate base of the DSI functions instead as a Brønsted-base, with the rate and stereodetermining step involving an enantioselective deprotonation of a Wheland intermediate. The experimental data was used to initiate a DFT exploration of the reaction mechanism, which after thorough analysis of the transition state structures and reaction coordinate confirmed our revised hypothesis. The unique structural features of the highest performing catalyst were explored further with a chemoinformatics derived workflow, leading to a highly detailed elucidation of those factors contributing to the origin of enantioselection.