RESUMEN
The dimerization of nitrogen monoxide (NO) is highly relevant in homo- and heterogeneous biochemical and environmental redox processes, but a broader understanding is challenged by the endergonic nature of this equilibrium. The present work describes NO-dimerization leveraged by structurally constrained aluminum and metal-ligand cooperativity at the anionic calix[4]pyrrolato aluminate(III). Quantum chemical calculations reveal the driving force for N-N bond formation, while reactivity tests shed light on subsequent redox chemistry and NO decomposition at metal surfaces. Inhibiting the dimerization pathway by saturating NO's unpaired electron with a phenyl group (nitrosobenzene) allows trapping the 1,2-adduct as a key intermediate. Elevated temperatures result in an unprecedented and high-yielding rearrangement of the calix[4]pyrrolato ligand scaffold. Kinetic and theoretical studies provide a comprehensive picture of the rearrangement mechanism and delineate systematics for ring modification of the prominent calix[4]pyrrole macrocycle.
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"How strong is this Lewis acid?" is a question researchers often approach by calculating its fluoride ion affinity (FIA) with quantum chemistry. Here, we present FIA49k, an extensive FIA dataset with 48,986 data points calculated at the RI-DSD-BLYP-D3(BJ)/def2-QZVPP//PBEh-3c level of theory, including 13 different p-block atoms as the fluoride accepting site. The FIA49k dataset was used to train FIA-GNN, two message-passing graph neural networks, which predict gas and solution phase FIA values of molecules excluded from training with a mean absolute error of 14â kJ mol-1 (r2=0.93) from the SMILES string of the Lewis acid as the only input. The level of accuracy is notable, given the wide energetic range of 750â kJ mol-1 spanned by FIA49k. The model's value was demonstrated with four case studies, including predictions for molecules extracted from the Cambridge Structural Database and by reproducing results from catalysis research available in the literature. Weaknesses of the model are evaluated and interpreted chemically. FIA-GNN and the FIA49k dataset can be reached via a free web app (www.grebgroup.de/fia-gnn).
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The quantification of Lewis acidity is of fundamental and applied importance in chemistry. However, if neutral and charged Lewis acids are compared, a coherent ranking has been elusive, and severe uncertainties were accepted. With this study, we present a systematic computational analysis of Lewis base affinities of 784 mono-, di- and tricationic Lewis acids and their comparison with 149 representative neutral Lewis acids. Evaluating vacuum fluoride ion affinities (FIA) reveals a charge-caused clustering that prohibits any meaningful ranking. Instead, solvation-corrected FIAsolv is identified as a metric that overcomes charge sensitivity in a balanced manner, allowing for a coherent evaluation of Lewis acidity across varying charge states. Analyzing the impact of molecular volume on solvation-induced FIA damping provides rationales for fundamental trends and guidelines for the choice or design of neutral and cationic Lewis acids in the condensed phase. Exploring alternative scales, explicit counteranion effects, and selected experimental case studies reaffirms the advantages of solvation-corrected FIAsolv as the most versatile and practical approach for the quantitative ranking of general (thermodynamic) Lewis acidity.
RESUMEN
Forcing a priori tetracoordinate atoms into planar configuration represents a promising concept for enhanced reactivity of p-block element-based systems. Herein, the synthesis, characterization, and reactivity of calix[4]pyrrolato gallates, constituting square planar-coordinated gallium(iii) atoms, are reported. Unusual structural constraint-induced Lewis acidity against neutral and anionic donors is disclosed by experiment and rationalized by computations. An energetically balanced dearomatization/rearomatization of a pyrrole unit enables fully reversible metal-ligand cooperative capture of CO2. While alcohols are found unreactive against the gallates, a rapid and selective OH-bond activation can be triggered upon protonation of the ligand. Secondary ligand-sphere modification adds a new avenue to structurally-constrained complexes that unites functional group tolerance with unconventional reactivity.
RESUMEN
The potential energy surfaces of 15 tetrahedral p-block element hydrides were screened on the multireference level. It was addressed whether stereoinversion competes against other reactions, such as reductive H2-elimination or hydride loss, and if so, along which pathway the stereomutation occurs. Importantly, stereoinversion transition structures for the ammonium cation (C4v) and the tetrahydridoborate anion (Cs) were identified for the first time. Revisiting methane's Cs symmetric inversion transition structure with the mHEAT+ protocol revealed an activation enthalpy for stereoinversion, in contrast to all earlier studies, which is 5 kJ mol-1 below the C-H bond dissociation enthalpy. Square planar structures were identified lowest in energy only for the inversion of AlH4 -, but a novel stepwise Cs-inversion was discovered for SiH4 or PH4 +. Overall, the present contribution delineates essentials of the potential energy surfaces of p-block element hydrides, while structure-energy relations offer design principles for the synthetically emerging field of structurally constrained compounds.
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TermodinámicaRESUMEN
High molar weight polyphosphinoboranes represent materials with auspicious properties, but their preparation requires transition metal-based catalysts. Here, calix[4]pyrrolato aluminate is shown to induce the dehydropolymerization of phosphine boranes to high molar mass polyphosphinoboranes (up to Mn =43 000â Da). Combined GPC and 31 P DOSY NMR spectroscopic analyses, quantum chemical computations, and stoichiometric reactions disclose a P-H bond activation by the cooperative action of the square-planar aluminate and the electron-rich ligand framework. This first transition metal-free catalyst for P-B dehydrocoupling overcomes the problem of residual d-block metal impurities in the resulting polymers that might interfere with the reproducibility of the properties for this emerging class of inorganic materials.
RESUMEN
The tetrahedron is the primary structural motif among the p-block elements and determines the architecture of our bio- and geosphere. However, a broad understanding of the configurational inversion of tetrahedral compounds is missing. Here, we report over 250 energies (DLPNO-CCSD(T)) for square planar inversion of third- and fourth-period element species of groups 13, 14, and 15. Surprisingly low inversion barriers are identified for compounds of industrial relevance (e.g., ≈100 kJ mol-1 for Al(OH)4 -). More fundamentally, the second-order Jahn-Teller theorem is disclosed as suitable to rationalize substituent and central element effects. Bond analysis tools give further insights into the preference of eight valence electron systems with four substituents to be tetrahedral. Hence, this study develops a model to understand, memorize, and predict the angular flexibility of tetrahedral species. Perceiving the tetrahedron not as forcingly rigid but as a dynamic structural entity might leverage new approaches and visions for adaptive matter.
RESUMEN
Calix[4]pyrroles are readily synthesized in one step from pyrroles and ketones. For several decades, these macrocycles have been exploited as powerful anion receptors or ligands for transition and rare-earth metals. In contrast, calix[4]pyrrolates as ligands for p-block elements were established only in 2018. The present feature article reviews these developments, together with the recent progress on s-, d-, and f-block element complexes of the calix[4]pyrroles. Particular focus is given on the calix[4]pyrrolato aluminate and the corresponding silane, both featuring square planar-coordinated p-block elements in their highest oxidation states. These unique "anti-van't-Hoff-Le-Bel" structures introduce valuable characteristics into main-group element chemistry, such as agostic interactions or ligand-to-metal charge transfer absorptions. The most vital reactivities are highlighted, which rely on properties ranging from amphoterism, redox-activity, and a small HOMO-LUMO gap up to the ability to provide a platform for additional external stimuli. Overall, these developments underscore the beneficial impact of structural constraint of p-block elements and element-ligand cooperativity to enhance the functionality of the most abundant elements in their native oxidation states.
RESUMEN
The vital effect of radical states on the pharmacological activity of phenothiazine-based drugs has long been speculated. Whereas cationic radicals of N-substituted phenothiazines show high stability, the respective neutral radicals of N-unsubstituted phenothiazines have never been isolated. Herein, the 1,9-diamino-3,7-di-tert-butyl-N1 ,N9 -bis(2,6-diisopropylphenyl)-10H-phenothiazin-10-yl radical (SQH2 . ) is described as the first air-stable, neutral phenothiazinyl free radical. The crystalline dark-blue species is characterized by means of EPR and UV/Vis/near-IR spectroscopy, as well as cyclic voltammetry, spectro-electrochemical analysis, single-crystal XRD, and computational studies. The SQH2 . radical stands out from other aminyl radicals by an impressive radical stabilization energy and its parent amine has one of the weakest N-H bond dissociation energies ever determined. In addition to serving as open-shell reference in medicinal chemistry, its tridentate binding pocket or hydrogen-bond-donor ability might enable manifold uses as a redox-active ligand or proton-coupled electron-transfer reagent.
RESUMEN
Most p-block metal amides irreversibly react with metal alkoxides when subjected to alcohols, making reversible transformations with OH-substrates a challenging task. Herein, we describe how the combination of a Lewis acidic square-planar-coordinated aluminum(iii) center with metal-ligand cooperativity leverages unconventional reactivity toward protic substrates. Calix[4]pyrrolato aluminate performs OH-bond activation of primary, secondary, and tertiary aliphatic and aromatic alcohols, which can be fully reversed under reduced pressure. The products exhibit a new form of metal-ligand cooperative amphoterism and undergo counterintuitive substitution reactions of a polar covalent Al-O bond by a dative Al-N bond. A comprehensive mechanistic picture of all processes is buttressed by isolation of intermediates, spectroscopy, and computation. This study delineates how structural constraints can invert thermodynamics for seemingly simple addition reactions and invert common trends in bond energies.