Neutral Adducts of Molybdenum Hexafluoride Structure and Bonding in MoF6(NC5H5) and MoF6(NC5H5)2.

The first Lewis acid base adducts of MoF6 and an organic base have been synthesized, i.e., MoF6(NC5H5) and MoF6(NC5H5)2. These adducts are structurally characterized with X-ray crystallography, showing that both adducts adopt capped trigonal prismatic structures. The MoF6(NC5H5) and MoF6(NC5H5)2 adducts are fluxional on the NMR time scale at room temperature. Two different fluorine environments could be resolved by 19F NMR spectroscopy at -80 °C for the 1:2 adduct, MoF6(NC5H5)2, whereas MoF6(NC5H5) remains fluxional at that temperature. Density functional theory (DFT) calculations aide the assignment of the infrared and Raman spectra. Natural Bond Order and Molecular Electrostatic Potential analyses elucidate the structures and properties of the MoF6 pyridine adducts. Regions of significantly higher molecular electrostatic potential, i.e., σ-holes, in trigonal prismatic compared to octahedral MoF6 rationalize the capped trigonal prismatic geometry of the adducts. Whereas MoF6(NC5H5) is stable at room temperature under exclusion of moisture, MoF6(NC5H5)2 decomposes at 60 °C in pyridine solvent, and the solid slowly decomposes at room temperature after 24 h.

Well-Defined Highly-Coordinated Copper(III) Iodide and Pincer Tris(trifluoromethyl)copper Complexes.

Copper(III) iodide and bromide complexes representing a unique combination of highly-coordinated metal and soft polarizable anions were synthesized and fully characterized, including X-ray crystallography. Ligand substitution in well-defined highly-coordinated copper complex PyCu(CF3)3 with pincer ligands was achieved to give formally octahedral copper(III) complexes.

Imidazole-Based Ionic Liquid Engineering for Perovskite Solar Cells with High Efficiency and Excellent Stability.

Despite the remarkable progress of perovskite solar cells (PSCs), the substantial inherent defects within perovskites restrict the achievement of higher efficiency and better long-term stability. Herein, we introduced a novel multifunctional imidazole analogue, namely, 1-benzyl-3-methylimidazolium bromide (BzMIMBr), into perovskite precursors to reduce bulk defects and inhibit ion migration in inverted PSCs. The electron-rich environment of -N- in the BzMIMBr structure, which is attributed to the electron-rich adjacent benzene ring-conjugated structure, effectively passivates the uncoordinated Pb2+ cations. Moreover, the interaction between the BzMIMBr additive and perovskite can effectively hinder the deprotonation of formamidinium iodide/methylammonium iodide (FAI/MAI), extending the crystallization time and improving the quality of the perovskite precursors and films. This interaction also effectively inhibits ion migration to subsequent deposited films, leading to a noteworthy decrease in trap states. Various characterization studies show that the BzMIMBr-doped films exhibit superior film morphology and surface uniformity and reduced nonradiative carrier recombination, consequently enhancing crystallinity by reducing bulk/surface defects. The PSCs fabricated on the BzMIMBr-doped perovskite thin film exhibit a power conversion efficiency of 23.37%, surpassing that of the pristine perovskite device (20.71%). Additionally, the added BzMIMBr substantially increased the hydrophobicity of perovskite, as unencapsulated devices still retained 93% of the initial efficiency after 1800 h of exposure to air (45% relative humidity).

Complexes of Zinc-Coordinated Heteroaromatic N-Oxides with Pyrene: Lewis Acid Effects on the Multicenter Donor-Acceptor Bonding.

4-Nitroquinoline-N-oxide (NQO) and 4-nitropyridine-N-oxide (NPO) are important precursors for the synthesis of substituted heterocycles while NQO is a popular model mutagen and carcinogen broadly used in cancer research; intermolecular interactions are critical for their reactions or functioning in vivo. Herein, the effects of the coordination of N-oxide's oxygen atom to Lewis acids on multicenter donor-acceptor bonding were explored via a combination of experimental and computational studies of the complexes of NQO and NPO with a typical π-electron donor, pyrene. Coordination with ZnCl2 increased the positive electrostatic potentials on the surfaces of these π-acceptors and lowered the energy of their LUMO. Analogous effects were observed upon the protonation of the N-oxides' oxygen or bonding with boron trifluoride. The interaction of ZnCl2, NPO, or NQO and pyrene resulted in the formation of dark co-crystals comprising π-stacked Zn-coordinated N-oxides and pyrene similar to that found with protonated or (reported earlier) BF3-bonded N-oxides. Computational studies indicated that the coordination of N-oxides to zinc(II), BF3, or protonation led to the strengthening of the multicenter bonding of the nitro-heterocycle with pyrene, and this effect was related both to the increased electrostatic attraction and molecular-orbital interactions in their complexes.

Structural Flexibility is a Decisive Factor in FLP Dihydrogen Cleavage with Tetrahedral Lewis Acids: A Silane Case Study.

Dihydrogen activation is the paradigmatic reaction of frustrated Lewis pairs (FLPs). While trigonal-planar Lewis acids have been well established in this transformation, tetrahedral Lewis acids are surprisingly limited. Indeed, several cases were computed as thermodynamically and kinetically feasible but exhibit puzzling discrepancies with experimental results. In the present study, a computational investigation of the factors influencing dihydrogen activation are considered by large ensemble sampling of encounter complexes, deformation energies and the activation strain model for a silicon/nitrogen FLP and compared with a boron/phosphorous FLP. The analysis adds the previously missing dimension of Lewis acids' structural flexibility as a factor that influences preexponential terms beyond pure transition state energies. It sheds light on the origin of "overfrustration" (defined herein), indicates structural constraint in Lewis acids as a linchpin for activation of weak donor substrates, and allows drawing a more refined mechanistic picture of this emblematic reactivity.

Revisiting the Mechanism of Asymmetric Ni-Catalyzed Reductive Carbo-Carboxylation with CO2: The Additives Affect the Product Selectivity.

The mechanistic details of the asymmetric Ni-catalyzed reductive cyclization/carboxylation of alkenes with CO2 have been revisited using DFT methods. Emphasis was put on the enantioselectivity and the mechanistic role of Lewis acid additives and in situ formed salts. Our results show that oxidative addition of the substrate is rate-limiting, with the formed Ni(II)-aryl intermediate preferring a triplet spin state. After reduction to Ni(I), enantioselective cyclization of the substrate occurs, followed by inner sphere carboxylation. Our proposed mechanism reproduces the experimentally observed enantiomeric excess and identifies critical C-H/O and C-H/N interactions that affect the selectivity. Further, our results highlight the beneficial effect of Lewis acids on CO2 insertion and suggest that in situ formed salts influence if the 5-exo or 6-endo product will be formed.

Lewis Acid Catalyzed Cyclopropane Ring-Opening-Cyclization Cascade Using Thioureas as a N,N-bisnucleophile: Synthesis of Bicyclic Furo-, Pyrano-, and Pyrrololactams via a Formal [4+1]-Addition.

Fused bicyclic cyclopropanes were converted by Lewis acid-catalysis with thioureas to furo-, pyrano, and pyrrololactams with yields of up to 99 % and high diastereoselectivity. The formation of the title compounds, representing a formal [4+1]-cycloaddition to a donor-acceptor substituted cyclopropane, follows a cascade reaction involving SN1-type ring-opening addition and cyclization. Thiourea, being a cost-effective and odorless reagent, acts as an N,N-bis-nucleophile to generate bicyclic compounds containing an N-substituted γ-lactam moiety.

Direct Access to Benzolactams and Benzolactones via Nickel Catalyzed Carbonylation with CO2.

A new nickel catalyzed cross-electrophile coupling for accessing γ-lactams (isoindolinones) as well as γ-lactones (isobenzofuranones) via carbonylation with CO2 is documented. The protocol exploits the synergistic role of redox-active Ni(II) complexes and AlCl3 as a CO2 activator/oxygen scavenger, leading to the formation of a wide range of cyclic amides and esters (28 examples) in good to high yields (up to 87 %). A dedicated computational investigation revealed the multiple roles played by AlCl3. In particular, the simultaneous transient protection of the pendant amino group of the starting reagents and the formation of the electrophilically activated CO2-AlCl3 adduct are shown to concur in paving the way for an energetically favorable mechanistic pathway.

Tridentate Lewis Acids Based on Tribenzotriquinacene Chalices.

Chalice-shaped tridentate poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Stannylation of the alkyne units, attached via phenyl-spacers to the benzhydrylic positions to the TBTQ scaffold, with Me2NSnMe3 afforded the trimethyltin substituted TBTQ derivative. Replacement of these tin functions with other elements resulted in rigid boron- and aluminium-functionalised PLAs. More flexible PLAs were obtained by hydrometallation reactions of the terminal alkyne groups of 4b,8b,12b-tris((ethynyl)phenyl)tribenzotriquinacene. The resulting poly-Lewis acids were tested for their acceptor abilities in host-guest experiments with suitable bases. Preliminary tests with pyridine led to the synthesis of a large tridentate base with three pyridyl groups attached to a TBTQ backbone. Complexation of this Lewis base with the PLAs resulted in the formation of aggregates, which were studied in solution in more detail by 1H DOSY NMR experiments regarding their size. Further experiments were performed with the tridentate bases 1,4,7-trimethyl-1,4,7-triazacyclononane and tris((dimethylphosphino)methyl)phenylsilane.

Tetrazole-Functionalized Organoboranes Exhibiting Dynamic Intramolecular N→B-Coordination and Cyanide-Selective Anion Binding.

Starting from two different cyano-functionalized organoboranes, we demonstrate that 1,3-dipolar [3+2] azide-nitrile cycloaddition can serve to generate libraries of alkyl-tetrazole-functionalized compounds capable of intramolecular N→B-Lewis adduct formation. Due to the relatively low basicity of tetrazoles, structures can be generated that exhibit weak and labile N→B-coordination. The reaction furnishes 1- and 2-alkylated regio-isomers that exhibit different effective Lewis-acidities at the boron centers, and vary in their optical absorption and fluorescence properties. Indeed, we identified derivatives capable of selectively binding cyanide over fluoride, as confirmed by 11B NMR. This finding demonstrates the potentialities of this synthetic strategy to systematically fine-tune the properties of lead structures that are of interest as chemical sensors.

Facile Energy Release from Substituted Dewar Isomers of 1,2-Dihydro-1,2-Azaborinines Catalyzed by Coinage Metal Lewis Acids.

Molecular solar thermal systems (MOST) represent an auspicious solution for the storage of solar energy. We report silver salts as a unique class of catalysts, capable of releasing the stored energy from the promising 1,2-dihydro-1,2-azaborinine based MOST system. Mechanistic investigations provided insights into the silver catalyzed thermal backreaction, concurrently unveiling the first crystal structure of a 2-aza-3-borabicyclo[2.2.0]hex-5-ene, the Dewar isomer of 1,2-dihydro-1,2-azaborinine. Quantification of activation energies by kinetic experiments has elucidated the advantageous energy change associated with Lewis acid catalysts, a phenomenon corroborated through computational analysis. By means of low temperature NMR spectroscopy, mechanistic insights into the coordination of Ag+ to the 1,2-dihydro-1,2-azaborinine were gained.

Synthesis of 1,3-Dibromopyrene as Precursor of 1-, 3-, 6-, and 8-Substituted Long-Axially Symmetric Pyrene Derivatives.

Pyrene derivatives bearing substituents at positions 1, 3, 6, and 8 find numerous applications, as exemplified by their use in lasers, sensors, and bioimaging probes. However, these derivatives typically have point-symmetric or short-axially symmetric structures, whereas long-axially symmetric derivatives remain underexplored because of the difficulty in obtaining their precursor, 1,3-dibromopyrene. To address this problem, we herein synthesized 1,3-dibromopyrene from 1-methoxypyrene in an overall yield (71 % over four steps) considerably exceeding those of existing methods. 1,3-Dibromopyrene was converted into 13OPA, a long-axially symmetric pyrene dye with electron-donor (alkoxy) groups at positions 1 and 3 and electron-acceptor (formyl) groups at positions 6 and 8. 13OPA exhibited photophysical properties distinct from those of its point-symmetric and short-axially symmetric isomers, featuring a broad and strongly redshifted absorption, strong fluorescence with reduced sensitivity to protic solvents, and small dipole moment change upon photoexcitation. The derivatization of 13OPA into a Schiff base and its functionalization via Lewis acid-base pairing were also demonstrated. Thus, our work expands the design scope of pyrene-based molecules, particularly those used as emitters.

Predicting Lewis Acidity: Machine Learning the Fluoride Ion Affinity of p-Block-Atom-Based Molecules.

"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 14 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 750 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).

Lewis Acid Decorated Hexacyanodiborane(6) Dianion.

First examples of diborane(6) dianions decorated with weakly coordination B(C6F5)3 (BCF) groups and SiEt3 + moieties have been synthesized demonstrating the synthetic potential of the [B2(CN)6]2- dianion. [B2{CNB(C6F5)3}6]2- (1) was isolated as potassium and tetrabutylammonium salt. 1 is a rare example for a weakly coordinating dianion and it was used for the stabilization of the carbocation [Ph3C]+ and the oxonium acid [H(OEt2)2]+. Reaction of [Ph3C]21 with HSiEt3 resulted in the silylated neutral diborane(6) [B2{CNB(C6F5)3}4(CNSiEt3)2] (2) in which two BCF groups have been selectively replaced by SiEt3 + substituents, underscoring the stability and chemical versatility of the [B2(CN)6]2- dianion. The chemical properties and physicochemical data of 1 and 2 provide insight into electronic, coordinating, and steric properties of theses novel diborane(6) compounds.

How to Deal with Charge in the Ranking of Lewis Acidity: Critical Evaluation of an Extensive Set of Cationic Lewis Acids.

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.

Selectivity in Adduct Formation of a Bidentate Boron Lewis Acid.

A bidentate boron Lewis acid based on 1,8-diethynylanthracene has been studied in detail with respect to its adduct formation with diamines and diphosphanes of different linker lengths between the donor functions. A clear correlation between the linker length of the bifunctional base and the formation of 1 : 1 adducts, 1 : 2 adducts or oligomers was found. The adducts were characterized in solution by NMR titration experiments and structurally by X-ray diffraction. In addition, adduct formation and competition experiments of the host system with ZR3 (Z=N, P; R=H, Me) demonstrated the generally higher stability of alkylphosphane adducts compared to alkylamine adducts with boron functions. The results provide a general insight into the adduct formation of bidentate Lewis acids with guests of different sizes as well as the differences in stability between borane-amine and borane-phosphane adducts.

Radical Reactions in Organic Synthesis: Exploring in-, on-, and with-Water Methods.

Radical reactions in water or aqueous media are important for organic synthesis, realizing high-yielding processes under non-toxic and environmentally friendly conditions. This overview includes (i) a general introduction to organic chemistry in water and aqueous media, (ii) synthetic approaches in, on, and with water as well as in heterogeneous phases, (iii) reactions of carbon-centered radicals with water (or deuterium oxide) activated through coordination with various Lewis acids, (iv) photocatalysis in water and aqueous media, and (v) synthetic applications bioinspired by naturally occurring processes. A wide range of chemical processes and synthetic strategies under different experimental conditions have been reviewed that lead to important functional group translocation and transformation reactions, leading to the preparation of complex molecules. These results reveal how water as a solvent/medium/reagent in radical chemistry has matured over the last two decades, with further discoveries anticipated in the near future.

Improved Process for the Continuous Acylation of 1,3-Benzodioxole.

The acylation of 1,3-benzodioxole was studied in a continuous process using a recyclable heterogeneous substoichiometric catalyst. In a short time period (30 min), at 100 °C, the conversion rate was 73%, with a selectivity of 62% of the desired acylated product; the reaction was run continuously for 6 h, showing excellent stability and selectivity. Moreover, the unreacted starting material, 1,3-benzodioxole, can be easily separated by distillation and recycled.

A Blueprint for Secondary Coordination Sphere Editing: Approaches Toward Lewis-Acid Assisted Carbon Dioxide Co-Activation.

Carbon dioxide (CO2) is a potent greenhouse gas of environmental concern. Seeking to offer a solution to the "CO2-problem", the chemistry community has turned a focus toward transition metal complexes which can activate, reduce, and convert CO2 into carbon-based products. The design of such systems involves judicious selection of both metal and accompanying donor ligand; in part, these efforts are motivated by biological metalloenzymes that undertake similar transformations. As a design element, metal-ligand cooperativity, which leverages intramolecular interactions between a transition metal and an adjacent secondary ligand site, has been acknowledged as a vitally important component by the CO2 activation community. These systems offer a "push-pull" style of activation where electron density is chaperoned onto CO2 with an accompanying electrophile, such as a Lewis-acid, playing the role of acceptor. This pairing allows for the stabilization of reactive CxHyOz-containing intermediates and can bias CO2 product selectivity. In the laboratory, chemists can test hypotheses and ideas, enabling rationalization of why a given pairing of transition metal/Lewis-acid leads to selective CO2 reduction outcomes. This Concept identifies literature examples and highlights key design properties, allowing interested contributors to design, create, and implement novel systems for productive transformations of a small molecule (CO2) with huge potential impact.

C-F Bond Insertion: An Emerging Strategy for Constructing Fluorinated Molecules.

C-F Insertion reactions, where an organic fragment formally inserts into a carbon-fluorine bond in a substrate, are highly attractive, yet largely unexplored, methods to prepare valuable fluorinated molecules. The inherent strength of C-F bonds and the resulting need for a large thermodynamic driving force to initiate C-F cleavage often leads to sequestering of the released fluoride in an unreactive by-product. Recently, however, several groups have succeeded in overcoming this challenge, opening up the study of C-F insertion as an efficient and highly atom-economical approach to prepare fluorinated compounds. In this article, the recent breakthroughs are discussed focusing on the key conceptual advances that allowed for both C-F bond cleavage and subsequent incorporation of the released fluoride into the product.