Formation Of Lewis Acid-base Adducts Research Articles

Asymmetric catalysis by chiral FLPs: A computational mini-review.

Steric hindrance in Lewis acid (LA) and Lewis base (LB) obstruct the Lewis acid-base adduct formation, and the pair was termed as frustrated Lewis pair (FLP). In the past 16years, the field of enantioselective catalysis by chiral FLPs has been slowly growing. It was shown that chiral LAs are significant as they are involved in the hydrogen transfer (HT) step to the imine, resulting in enantioselectivity. After H2 activation, the borohydride can exist in a number of plausible conformations and their stability is governed by the presence of noncovalent interaction through C-H····π and π····π interactions. However, LBs are not ideal for asymmetric induction as they compete with the imine substrate as a counter LB. Further, the proton transfer from chiral LB to the imine does not induce any chirality as chirality develops in the HT step. However, intramolecular FLPs with chiral scaffold are very efficient as they possess an optimum distance between LA and LB, which facilitates the H2 activation but precludes the adduct formation of the small molecules substrate with the LA component. This mini-review summarizes computational investigation involving chiral LA and LB, and discusses intramolecular FLPs in the enantioselective catalysis.

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

In chloroform solution, the reaction of bis(tert-butylamino)dimethylsilane ((tBuNH)2SiMe2) and an α-amino acid (α-amino isobutyric acid, H2Aib; D-phenylglycine, H2Phg; L-valine, H2Val) in the presence of N-methylimidazole (NMI) gave rise to the formation of the pentacoordinate silicon complexes (Aib)SiMe2-NMI, (Phg)SiMe2-NMI and (Val)SiMe2-NMI, respectively. Therein, the amino acid building block was a di-anionic bidentate chelator at the silicon atom. In solution, the complexes were involved in rapid coordination–dissociation equilibria between the pentacoordinate Si complex (e.g., (Aib)SiMe2-NMI) and its constituents NMI and a five-membered silaheterocycle (e.g., (Aib)SiMe2), as shown by 29Si NMR spectroscopy. The energetics of the Lewis acid-base adduct formation and the competing solvation of the NMI molecule by chloroform were assessed with the aid of computational methods. In CDCl3 solution, deuteration of the silaheterocycle NH group proceeded rapidly, with more than 50% conversion within two days. Upon cooling to −44 °C, the chloroform solvates of the adducts (Aib)SiMe2-NMI and (Phg)SiMe2-NMI crystallized from their parent solutions and allowed for their single-crystal X-ray diffraction analyses. In both cases, the Si atom was situated in a distorted trigonal bipyramidal coordination sphere with equatorial Si–C bonds and an equatorial Si–N bond (the one of the silaheterocycle). The axial positions were occupied by a carboxylate O atom of the silaheterocycle and the NMI ligand’s donor-N-atom.

Functionalization of antimonene and bismuthene with Lewis acids.

Elemental 2D pnictogens (group 15) are an interesting class of materials with tunable band structures and high carrier mobilities. Heavier pnictogens (Sb and Bi) are stable under ambient conditions compared to lighter members (P and As) and are emerging as interesting candidates for various electronic and optoelectronic applications. The reactivity of these materials is due to the presence of a lone pair which can be effectively utilized to tune material properties via different functionalization strategies. In this work, we have synthesized antimonene and bismuthene nanosheets by liquid exfoliation which are emissive in the visible range and functionalized these nanosheets with group 12 and 13 Lewis acids (ZnCl2, CdCl2, BCl3, GaCl3, AlCl3, and InCl3). Interaction of these Lewis acids with the lone pairs on Sb/Bi leads to the formation of Lewis acid-base adducts with the corresponding changes in the bonding environment along with lattice distortion and rehybridization of the band structure. Interestingly, the changes in band structure upon functionalization were realized as a blue shift in the emission of few-layered Sb and Bi. This is the first report on the functionalization of heavier pnictogens by the formation of Lewis acid-base adducts and opens a path for tuning their properties for integration in electronic and optoelectronic devices.

Binding Properties of a Dinuclear Zinc(II) Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of Lewis Acid-Base Adducts with Diamines

In this paper we report the binding properties, by combined 1H NMR, optical absorption, and fluorescence studies, of a molecular tweezer composed of two Zn(salen)-type Schiff-base units connected by a flexible spacer, towards a series of ditopic diamines having a strong Lewis basicity, with different chain length and rigidity. Except for the 1,2-diaminoethane, in all other cases the formation of stable 1:1 Lewis acid-base adducts with large binding constants is demonstrated. For α,ω-aliphatic diamines, binding constants progressively increase with the increasing length of the alkyl chain, thanks to the flexible nature of the spacer and the parallel decreased conformational strain upon binding. Stable adducts are also found even for short diamines with rigid molecular structures. Given their preorganized structure, these latter species are not subjected to loss of degrees of freedom. The binding characteristics of the tweezer have been exploited for the colorimetric and fluorometric selective and sensitive detection of piperazine.

Lewis-Acid Doping of Triphenylamine-Based Hole Transport Materials Improves the Performance and Stability of Perovskite Solar Cells.

Highly efficient perovskite solar cells (PSCs) fabricated in the classic n-i-p configuration generally employ triphenylamine-based hole-transport layers (HTLs) such as spiro-OMeTAD, PTAA, and poly-TPD. Controllable doping of such layers has been critical to achieve increased conductivity and high device performance. To this end, LiTFSI/tBP doping and subsequent air exposure is widely utilized. However, this approach often leads to low device stability and reproducibility. Departing from this point, we introduce the Lewis acid tris(pentafluorophenyl)borane (TPFB) as an effective dopant, resulting in a significantly improved conductivity and lowered surface potential for triphenylamine-based HTLs. Here, we specifically investigated spiro-OMeTAD, which is the most widely used HTL for n-i-p devices, and revealed improved power conversion efficiency (PCE) and stability of the PSCs. Further, we demonstrated the applicability of TPFB doping to other triphenylamine-based HTLs. Spectroscopic characterizations reveal that TPFB doping results in significantly improved charge transport and reduced recombination losses. Importantly, the TPFB-doped perovskite devices retained near 85% of the initial PCE after 1000 h of storage in the air, while the conventional LiTFSI-doped device dropped to 75%. Finally, we give insight into utilizing other similar molecular dopants such as fluorine-free triphenylborane and phosphorus-centered tris(pentafluorophenyl)phosphine (TPFP) by density functional theory analysis underscoring the significance of the central boron atom and fluorination in TPFB for the formation of Lewis acid-base adducts.

Towards understanding the doping mechanism of organic semiconductors by Lewis acids.

Precise doping of organic semiconductors allows control over the conductivity of these materials, an essential parameter in electronic applications. Although Lewis acids have recently shown promise as dopants for solution-processed polymers, their doping mechanism is not yet fully understood. In this study, we found that B(C6F5)3 is a superior dopant to the other Lewis acids investigated (BF3, BBr3 and AlCl3). Experiments indicate that Lewis acid-base adduct formation with polymers inhibits the doping process. Electron-nuclear double-resonance and nuclear magnetic resonance experiments, together with density functional theory, show that p-type doping occurs by generation of a water-Lewis acid complex with substantial Brønsted acidity, followed by protonation of the polymer backbone and electron transfer from a neutral chain segment to a positively charged, protonated one. This study provides insight into a potential path for protonic acid doping and shows how trace levels of water can transform Lewis acids into powerful Brønsted acids.

Crystallization and grain growth regulation through Lewis acid-base adduct formation in hot cast perovskite-based solar cells

The precise control of perovskite crystallization process that could provide smooth films with large grains is a prerequisite for solar cell fabrication to achieve higher efficiencies. To regulate this crystallization process and to achieve it multiple times remains a humongous challenge. This process has been reproducibly demonstrated here through efficient molecular exchange via a Lewis acid-base adduct formation. In this work, a Lewis acid-base adduct approach in concurrence with hot casting technique was employed to efficiently control the perovskite crystallization by judiciously adding dimethyl sulfoxide (DMSO) to a precursor solution of lead iodide (PbI 2 ) and methyl ammonium chloride (MACl) in dimethylformamide (DMF). High quality perovskite films were fabricated by precisely controlling the volume of DMSO which resulted in low recombination rate and which had better light harvesting ability. Uniform films of MAPbCl x I 3-x having large grain size were formed reproducibly on addition of 1.5 equivalents (eq.) DMSO to the precursor solution. Perovskite solar cells fabricated using this solution resulted in maximum power conversion efficiency (PCE) of 14.11% with enhanced stability as compared to the reduced PCE values obtained with other DMSO ratios and pure DMF solution cast films. • Hot casting using Lewis acid-base approach resulted in large grain perovskite. • 1.5 equivalents of Lewis base (DMSO) gave largest grain size and smooth film. • A power conversion efficiency >14% achieved in inverted perovskite solar cell. • This method also improved the overall stability of the solar cells.

Enhanced Lewis acid-base adducts in doped stanene: Sensing and photocatalysis

Stanene is a quantum spin Hall insulator and a promising material for optoelectronic and electronic devices. Density functional theoretical (DFT) calculations are performed to understand the effect of elemental doping (In, Sb, and InSb) towards gas sensor and photocatalytic applications. The In/Sb doping in stanene enhances the formation of Lewis acid-base adducts with N-based gas molecules, which in turn improves the sensitivity and selectivity towards a particular gas molecule. Moreover, such stanene based systems show excellent energetic, thermal, dynamical, and mechanical stability and band edge potential, which further suggests that they can be synthesized and used for various applications.

Investigation of the Lewis acidic behaviour of an oxygen-bridged planarized triphenylborane toward amines and the properties of their Lewis acid-base adducts.

Lewis acid behavior of an oxygen-bridged triphenylborane (1) to amines and the properties of Lewis acid-base adducts of 1 with amines have been investigated. UV-vis titration and 11B NMR experiments showed the formation of Lewis acid-base adducts of 1 with pyridine, DMAP, quinuclidine, and DABCO, respectively (1·amine). X-ray crystallographic analysis revealed that the planar shape of 1 was converted to a bowl shape by the formation of 1·amine. Interestingly, 1·quinuclidine, 12·DABCO, and 1·DABCO exhibited dual emissions. Excitation spectra and photoluminescence decay time measurements suggest that the dual emissions were ascribed to two excited species, i.e., [1·amine]* and [1]* generated by photodissociation in the excited states.

Facile reduction of carboxylic acids to primary alcohols under catalyst-free and solvent-free conditions.

We report the development of a facile protocol for the deoxygenative hydroboration of aliphatic and aryl carboxylic acids to afford corresponding primary alcohols under solvent-free and catalyst-free conditions. The reaction proceeds under ambient temperature exhibits good tolerance towards various functional groups and generates quantitative yields. The plausible mechanism involves the formation of Lewis acid-base adducts as well as the liberation of hydrogen gas.

Interfacial Lewis Acid-Base Adduct Formation Probed by Vibrational Spectroscopy.

Understanding Lewis pair (LP) interactions at heterogeneous environments is important for controlling surface reactions. We report the formation of interfacial Lewis adducts with tris(pentafluorophenyl)borane as the Lewis acid and 4-mercaptobenzonitrile attached to gold as the Lewis base. We use the nitrile vibrational frequency as a probe of adduct strength, with stronger adducts leading to larger frequencies. The vibrational frequency shifts of the surface adducts were measured via sum frequency generation spectroscopy and compared to the frequency shifts of bulk adducts. Our results show a distinctly smaller frequency shift for the surface adducts compared to the bulk, indicating a weaker Lewis acid-base interaction near the surface. We explore three possible origins of this difference: interfacial frustration, surface electric fields, and electronic energy level alignment. We highlight the relevance of each and note that likely more than one of them affect the observed surface LP interactions.

Communication—A Phosphorus Pentafluoride Scavenger to Suppress Solid Electrolyte Interphase Damage at Moderately Elevated Temperature

We demonstrate that lithium/silicon monoxide (SiO) cell failure can be hindered by utilizing a Lewis-basic tris(2,2,2-trifluoroethyl) phosphite (TTFP), as an electrolyte additive. In the absence of TTFP, the solid electrolyte interphase (SEI) on the SiO electrode is attacked by Lewis-acidic phosphorus pentafluoride (PF5) generated by thermal decomposition of lithium hexafluorophosphate (LiPF6) at moderately elevated temperature. The SEI damage is followed by electrolyte decomposition/film deposition on the damaged electrode surface causing film growth, which leads to severe cell polarization and eventual failure. Conversely, effective PF5 scavenging by TTFP through Lewis acid-base adduct formation decreases SEI damage and thus hinders cell failure.

Evidence for Cation-Controlled Excited-State Localization in a Ruthenium Polypyridyl Compound.

The visible absorption and photoluminescence (PL) properties of the four neutral ruthenium diimine compounds [Ru(bpy)2(dcb)] (B2B), [Ru(dtb)2(dcb)] (D2B), [Ru(bpy)2(dcbq)] (B2Q), and [Ru(dtb)2(dcbq)] (D2Q), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO2(-))2-bpy, dtb is 4,4'-(tert-butyl)2-bpy, and dcbq is 4,4'-(CO2(-))2-2,2'-biquinoline, are reported in the presence of Lewis acidic cations present in fluid solutions at room temperature. In methanol solutions, the measured spectra were insensitive to the presence of these cations, while in acetonitrile a significant red shift in the PL spectra (≤1400 cm(-1)) was observed consistent with stabilization of the metal-to-ligand charge transfer (MLCT) excited state through Lewis acid-base adduct formation. No significant spectral changes were observed in control experiments with the tetrabutylammonium cation. Titration data with Li(+), Na(+), Mg(2+), Ca(2+), Zn(2+), Al(3+), Y(3+), and La(3+) showed that the extent of stabilization saturated at high cation concentration with magnitudes that scaled roughly with the cation charge-to-size ratio. The visible absorption spectra of D2Q was particularly informative due to the presence of two well-resolved MLCT absorption bands: (1) Ru → bpy, λmax ≈ 450 nm; and (2) Ru → dcbq, λmax ≈ 540 nm. The higher-energy band blue-shifted and the lower-energy band red-shifted upon cation addition. The PL intensity and lifetime of the excited state of B2B first increased with cation addition without significant shifts in the measured spectra, behavior attributed to a cation-induced change in the localization of the emissive excited state from bpy to dcb. The importance of excited-state localization and stabilization for solar energy conversion is discussed.

Conceptual quantum chemical analysis of bonding and noncovalent interactions in the formation of frustrated Lewis pairs.

The contributions of covalent and noncovalent interactions to the formation of classical adducts of bulky Lewis acids and bases and frustrated Lewis pairs (FLPs) were scrutinized by using various conceptual quantum chemical techniques. Significantly negative complexation energies were calculated for fourteen investigated Lewis pairs containing bases and acids with substituents of various sizes. A Ziegler-Rauk-type energy decomposition analysis confirmed that two types of Lewis pairs can be distinguished on the basis of the nature of the primary interactions between reactants; dative-bond formation and concomitant charge transfer from the Lewis base to the acid is the dominant and most stabilizing factor in the formation of Lewis acid-base adducts, whereas weak interactions are the main thermodynamic driving force (>50 %) for FLPs. Moreover, the ease and extent of structural deformation of the monomers appears to be a key component in the formation of the former type of Lewis pairs. A Natural Orbital for Chemical Valence (NOCV) analysis, which was used to visualize and quantify the charge transfer between the base and the acid, clearly showed the importance and lack of this type of interaction for adducts and FLPs, respectively. The Noncovalent Interaction (NCI) method revealed several kinds of weak interactions between the acid and base components, such as dispersion, π-π stacking, C-H⋅⋅⋅π interaction, weak hydrogen bonding, halogen bonding, and weak acid-base interactions, whereas the Quantum Theory of Atoms in Molecules (QTAIM) provided further conceptual insight into strong acid-base interactions.

Silaimidazolium and silaimidazolidinium ions

2-Silaimidazolium ions and 2-silaimidazolidinium ions were synthesized by Lewis acid-base adduct formation between N-heterocyclic silylenes and silyl arenium ions. They were isolated in high yields as their [B(C(6)F(5))(4)](-) salts. These salts are stable at room temperature and were characterized by NMR spectroscopy supported by the results of density functional computations of molecular structures and NMR chemical shifts. NICS calculations suggest for the imidazolium ions only a modest degree of aromaticity. Despite the bulkiness of the used substituents R(1) and R(2), silylium ions and behave as classical Lewis pairs and show no unexpected reactivity.

Facile Splitting of Hydrogen and Ammonia by Nucleophilic Activation at a Single Carbon Center

In possessing a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble transition metal centers and thus could potentially mimic their chemical behavior. Although singlet di(amino)carbenes are inert toward dihydrogen, it is shown that more nucleophilic and electrophilic (alkyl)(amino)carbenes can activate H2 under mild conditions, a reaction that has long been known for transition metals. However, in contrast to transition metals that act as electrophiles toward dihydrogen, these carbenes primarily behave as nucleophiles, creating a hydride-like hydrogen, which then attacks the positively polarized carbon center. This nucleophilic behavior allows these carbenes to activate NH3 as well, a difficult task for transition metals because of the formation of Lewis acid-base adducts.

Boron–Nitrogen Adducts of 1,3,5‐Triaza‐7‐phosphaadamantane (PTA): Synthesis, Reactivity, and Molecular Structure

AbstractAddition of BH3 to 1,3,5‐triaza‐7‐phosphaadamantane (PTA) leads to the formation of the first coordination complex of PTA in which a nitrogen and not the phosphorus of PTA is involved in the bonding. Multinuclear NMR spectroscopy, X‐ray crystallography, and computational chemistry are utilized in the characterization of the products. Crystal structures of PTA–BH3 (1) and O=PTA–BH3 (2) adducts are described. In addition a coordination polymer, [CpRu(PTA)2Cl(Ph3B3O3)]n (3), resulting from Lewis acid–base adduct formation between the PTA ligands of CpRu(PTA)2Cl and the product of the cyclocondensation of phenylboronic acid is described. The polymeric compound 3 was also characterized by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Heterobimetallic bismuth–transition metal coordination complexes as single-source molecular precursors for the formation of advanced oxide materials

Abstract In this manuscript we outline recent results on the synthesis of heterobimetallic coordination complexes involving bismuth and the transition elements using either bifunctional ligands or Lewis acid–base adduct formation as a synthetic strategy. Significant structural features in the molecular heterobimetallic species resulting from these two approaches are highlighted. The ability of these complexes to act as single-source precursors for the formation of advanced oxide nanomaterials has been investigated, and the potential of these complexes versus traditional methods for the formation of advanced ceramics is discussed. To cite this article: T. Ould-Ely et al., C. R. Chimie 8 (2005) .

New heterometallic copper zinc alkoxides: synthesis, structure properties and pyrolysis to Cu/ZnO composites

The copper compound [(THF)KCu(O t Bu) 3] ∞ 1 was obtained by interaction of a 1:1 mixture of ZnCl 2/CuCl 2 with KO t Bu. Bi- and trifunctional aminoalcohols were used to synthesize the intramolecularly donor stabilized Cu(II) alkoxides Cu(OCH(R)CH 2NMe 2) 2 ( 3: R=Me, 4: =CH 2NMe 2) where 4 was structurally characterized. Lewis acid–base adduct formation with (Me 3Si) 3CZnCl gave the heterodinuclear compounds (Me 3Si) 3CZnCl · Cu(OCH(R)CH 2NMe 2) 2 ( 5: R=Me, 6: R=CH 2NMe 2), which were characterized by X-ray single-crystal structure analysis. The two metal centers Cu and Zn of 5 and 6 are bridged by two oxygen atoms to form a Cu–O–Zn core. Pyrolysis of compounds 5 and 6 in dry argon or a H 2/N 2 mixture at atmospheric pressure forms metallic copper and zinc oxide, whereas pyrolysis under O 2/Ar forms additionally oxidized copper species. Elemental analysis of the pyrolysis products showed carbon and nitrogen contamination. Scanning electron microscopy and energy dispersive X-ray analysis were performed to get information on the morphology and the chemical composition of the pyrolysis products.

Ligand additivity in 47-electron clusters. Electrochemistry of ( μ-H)Ru 3( μ3- η3-XCCRCR′)(CO) 9− n(PPh 3) n and reactions with electrophiles: one-electron oxidation and adduct formation

Reactions of clusters HRu 3( μ 3- η 3-XCCRCR′)(CO) 9− n (PPh 3) n (X=OMe, R=R′=Me, n=1, 2, 3; X=MeO, R=H, R′=EtO, n=2, 3; X=Et 2N, R=H, R′=Me, n=1, 2) with electrophilic reagents proceed either by 1-electron transfer or by Lewis acid-base adduct formation. The HOMO for the cluster series is Ru–Ru bonding with contributions from all three Ru atoms. Cyclic voltammograms of HRu 3( μ 3- η 3-XCCRCR′)(CO) 9− n (PPh 3) n ( n=2, 3) display in each case an electrochemically reversible to quasi-reversible, 1-electron oxidation, followed by an irreversible, 1-electron oxidation at a significantly more positive potential. The potential for the first oxidation is lowered both by an increasing degree of PPh 3 substitution and an increasing pi donor capability of the allylidene substituents. The dependence of the oxidation potential upon substitution of the metal and carbon framework atoms is analyzed as an example of ligand additivity in cluster systems. Radical cations derived from the di- and tri-substituted 1,3-dimetalloallyl clusters can be generated by oxidation with tris(4-bromophenyl)aminium hexachloroantimonate. These radical cations decompose within a few minutes at room temperature but are stable for long periods at temperatures below −40°C. Electrophilic addition of E=H 1+, Ag 1+ or Au(PPh 3) 1+ to the Ru–Ru bonds is observed. Adducts [ERu 3H( μ 3- η 3-XCCRCR′)(CO) 9− n (PPh 3) n ] 1+ have been characterized by IR and 1H- and 31P-NMR spectroscopies. The Au(PPh 3) moiety is found to bridge two or three Ru–Ru bonds in these adducts. Substitutional isomerism is induced by electrophilic addition.