Redox-Active Lewis Pairs Yield Diradicaloids and Enable Modular Control of the Diradical Character.

Stable metal-free diradicaloids are fascinating compounds, typically based on covalent polycyclic or nitrogen-containing π-conjugated frameworks. Unfortunately, their preparation and the modulation of their diradical character require substantial synthetic efforts. The present work introduces a synthetic approach to diradicaloids by the ease and modularity of Lewis pair formation. Binding redox-active bis(catecholato)silane Lewis acids to ditopic tetraoxolene Lewis bases yields adducts with varying spin ground states. Computational analyses disclose that the diradical character increases with the electron donor ability of the catechols and the electron accepting ability of the tetraoxolene. Hence, this protocol grants access to diradicaloids with rationally adjustable diradical character of high potential for numerous applications in a single step.

Dihydrogen Activation with a Neutral, Intermolecular Silicon(IV)-Amine Frustrated Lewis Pair.

The heterolytic cleavage of dihydrogen constitutes the hallmark reaction of frustrated Lewis pairs (FLP). While being well-established for planar Lewis acids, such as boranes or silylium ions, the observation of the primary H2 splitting products with non-planar Lewis acid FLPs remained elusive. In the present work, we report bis(perfluoro-N-phenyl-ortho-amidophenolato)silane and its application in dihydrogen activation to a fully characterized hydridosilicate. The strict design of the Lewis acid, the limited selection of the Lewis base, and the distinct reaction conditions emphasize the narrow tolerance to achieve this fascinating process with a tetrahedral Lewis acid.

Silicon Carbamates by CO2 Fixation: Brønsted Acid Labile Precursor of a Lewis Superacid.

Treatment of Lewis superacidic Si(catCl)2(MeCN)2 and tetramethylpiperidine (TMP) or hexahydropyrimidopyrimidine (hppH) with CO2 leads to an FLP-type formation of silicon carbamates. The employed Lewis base determines the hapticity at silicon and the reactivity of the carbamates in subsequent transformations. Upon treatment with a Brønsted acid, the carbamates liberate CO2 and reactivate the Lewis superacidic behavior of 1. Hence, the CO2 fixation products serve as valuable surrogates for Si(catCl)2 that circumvent its insolubility in organic solvents. Quantum chemical computations support all of the experimental observations.

Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis.

Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon-based reactions. However, their short-lived nature rendered even spectroscopic observations highly challenging. Here, we characterize hypercoordinated silicon anions, including the first bromido-, iodido-, formato-, acetato-, triflato- and sulfato-silicates. This is enabled by a new, donor-free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural, and computational insights allow a reassessment of Gutmann's empirical rules for the role of silicon hypercoordination in synthesis and catalysis. The electronic perturbations of 1 exerted on the bound anions indicate pronounced substrate activation.

Calix[4]pyrrolato Aluminate Catalyzes the Dehydrocoupling of Phenylphosphine Borane to High Molar Weight Polymers.

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 =43 000 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.

The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond.

Catechols occupy a unique role in the structural, bio-, and geochemistry of silicon. Although a wealth of knowledge exists on their hypercoordinate complexes, the structure of tetracoordinate bis(catecholato)silane, Si(catH)2 1, has been enigmatic since its first report in 1951. Indeed, the claim of a planar-tetracoordinated silicon in 1 triggered a prominent debate, which is unsettled to this day. Herewith, we present a comprehensive structural study on 1 and derivatives in the gas phase by electron diffraction, in a neon matrix by IR spectroscopy, in solution by diffusion NMR spectroscopy, and in the solid-state by X-ray diffraction and MAS NMR spectroscopy, complemented by high-level quantum-chemical computations. The compound exhibits unprecedented phase adaptation. In the gas phase, the monomeric bis(catecholato)silane is tetrahedral, but in the condensed phase, it is metastable toward oligomerization up to a degree controllable by the type of catechol, temperature, and concentration. For the first time, spectroscopic evidence is obtained for a rapid Si-O σ-bond metathesis reaction. Hence, this study sorts out a long-lasting debate and confirms dynamic covalent features for our Earth's crust's most abundant chemical bond.

An Air-Stable, Neutral Phenothiazinyl Radical with Substantial Radical Stabilization Energy.

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.

[Si(O2 C6 F4 )2 ]14 : Self-Assembly of a Giant Perfluorinated Macrocyclic Host by Low-Barrier Si-O Bond Metathesis.

The dynamic covalent self-assembly of 14 units of bis(perfluorocatecholato)silane leads to [Si(O2 C6 F4 )2 ]14 -the first giant perfluorinated macrocycle. The oligomerization process is monitored spectroscopically, and the macrocycle analyzed by single-crystal X-ray diffraction. The molecule forms a rigid cavity that can host two o-closo-dodecacarboranes. Computations rationalize the consistent and reproducible formation of the 14mer and disclose a non-catalyzed Si-O/ Si-O σ-bond metathesis with an exceptionally low energetic barrier. For the first time, the most prevalent linker in our geosphere-SiO4 -is disposed to construct a shape-defined crystalline macromolecule.

Bis(perchlorocatecholato)silane and heteroleptic bidonors: hidden frustrated Lewis pairs resulting from ring strain.

Bis(perchlorocatecholato)silane and bidentate N,N- or N,P-heteroleptic donors were reacted to form hexacoordinated complexes. Depending on the ring strain and hemilability in the adducts, frustrated Lewis pair (FLP) reactivity with aldehydes and catalytic ammonia borane dehydrocoupling was enabled. All reactions were analyzed using density functional theory. This approach represents an alternative way, beyond relying on steric bulk, to achieve frustration in bimolecular FLPs.

Bis(catecholato)silanes: assessing, rationalizing and increasing silicon's Lewis superacidity.

Although bis(catecholato)silanes have been known for several decades, their substantial Lewis acidity is not yet well described in the literature. Herewith, the synthesis and characterization of multiple substituted bis(catecholato)silanes and their triethylphosphine oxide, fluoride and chloride ion adducts are reported. The Lewis acidity of bis(catecholato)silanes is assessed by effective (Gutmann-Beckett, catalytic efficiency), global (theoretical and relative experimental fluoride (FIA) and chloride (CIA) ion affinities) and intrinsic (electrophilicity index) scaling methods. This comprehensive set of experimental and theoretical results reveals their general Lewis acidic nature and provides a consistent Lewis acidity trend for bis(catecholato)silanes for the first time. All experimental findings are supported by high-level DLPNO-CCSD(T) based thermochemical data and the Lewis acidity is rationalized by complementary chemical bonding analysis tools. Against the common belief that inductive electron withdrawal is the most important criterion for strong Lewis acidity, the present work highlights the decisive role of π-back bonding effects in aromatic ring systems to enhance electron deficiency. Thus, bis(perbromocatecholato)silane is identified and synthesized as the new record holder for silicon Lewis superacids.

Letalidade do extrato de synadenium grantii hook. F. (Euphorbiaceae) frente a caramujos biomphalaria glabrata say, 1818 (gastropoda, planorbidae) / Letalidad del extracto de synadenium grantii hook. F. (Euphorbiaceae) contra caracoles biomphalaria glabrata say, 1818 (gastropoda, planorbidae) / Lethality of synadenium grantii hook. F. (Euphorbiaceae) extract to snails biomphalaria glabrata say, 1818 (gastropoda, planorbidae)

No Brasil, o caramujo Biomphalaria glabrata Say, 1818 (Gastropoda, Planorbidae) atua como principal vetor hospedeiro intermediário do helminto trematódeo Schistosoma mansoni (Schistosomatidae), agente etiológico da esquistossomose. O combate deste hospedeiro com substâncias moluscicidas é considerado uma das formas de redução do risco de transmissão da esquistossomose. Na busca por novos produtos naturais para controlar este vetor, o presente trabalho testou os extratos de algumas espécies vegetais exóticas consideradas tóxicas: Allamanda cathartica L. (Apocynaceae), Breynia nivosa (W. Bull) Small (Phyllanthaceae), Croton floribundus Spreng. (Euphorbiaceae), Dieffenbachia picta Schott (Araceae), Euphorbia milii des Mol. var. breonii (Euphorbiaceae), Jatropha curcas L. (Euphorbiaceae), Monstera deliciosa Liebm. (Araceae) e Synadenium grantii Hook. f. (Euphorbiaceae). Apenas a espécie S. grantii apresentou atividade moluscicida (CL50 = 40,0 µg mL-1) promissora, sendo este o primeiro relato desta atividade para espécies do gênero Synadenium.

In Brazil, Biomphalaria glabrata Say, 1818 (Gastropoda, Planorbidae) snail serves as the principal intermediate vector host of Schistosoma mansoni (Schistosomatidae) trematode helminth, the etiologic agent of schistosomiasis. A way of reducing transmission risk of schistosomiasis is the combat of this host with molluscicide substances. In the search for new natural products to control this vector, the present study tested the extracts of some exotic plant species considered toxic: Allamanda cathartica L. (Apocynaceae), Breynia nivosa (W. Bull) Small (Phyllanthaceae), Croton floribundus Spreng. (Euphorbiaceae), Dieffenbachia picta Schott (Araceae), Euphorbia milii des Mol. var. breonii (Euphorbiaceae), Jatropha curcas L. (Euphorbiaceae), Monstera deliciosa Liebm. (Araceae) and Synadenium grantii Hook. f. (Euphorbiaceae). Only the S. grantii species showed molluscicide activity promising (LC50 = 40.0 mg mL-1), and this is the first report of this activity to the genus Synadenium (Euphorbiaceae).

En Brasil, el caracol Biomphalaria glabrata Say, 1818 (Gastropoda, Planorbidae) actúa como principal vector hospedero intermediario del helmintos trematodo Schistosoma mansoni (Schistosomatidae), agente etiológico de la esquistosomiasis. El combate de este hospedero con sustancias molusquicidas es considerado una de las formas de reducción del riesgo de transmisión de la esquistosomiasis. En la búsqueda por nuevos productos naturales para el control de este vector, el presente estudio examinó los extractos de algunas especies exóticas de plantas consideradas tóxicas: Allamanda cathartica L. (Apocynaceae), Breynia nivosa (W. Bull) Small (Phyllanthaceae), Croton floribundus Spreng. (Euphorbiaceae), Dieffenbachia picta Schott (Araceae), Euphorbia milii des Mol. var. breonii (Euphorbiaceae), Jatropha curcas L. (Euphorbiaceae), Monstera deliciosa Liebm. (Araceae) y Synadenium grantii Hook. f. (Euphorbiaceae). Sólo la especie S. grantii presentó actividad molusquicida prometedores (CL50 = 40,0 ug mL-1) promisora, siendo éste el primer relato de esta actividad para especies del género Synadenium.