Tuning the Lewis Acidity of Boranes in Frustrated Lewis Pair Chemistry: Implications for the Hydrogenation of Electron‐Poor Alkenes

An analysis of the metal‐free reduction of electron deficient olefins by frustrated Lewis pairs indicates that the rate‐determining step might be either the heterolytic cleavage of H₂ to form an ‐onium borohydride salt, or the subsequent transfer of the hydride moiety to the substrate following a Michael‐type addition reaction. While the use of strong Lewis acids such as B(C₆F₅)₃ facilitates the first of these processes, hydride transfer to the olefin should be contrarily favoured by the use of weak Lewis acids which, for this very same reason, might be unable to promote the prior H₂ split. After systematic testing of several boranes of different Lewis acidity (assessed by using the Childs’ method) and steric demand, an optimal situation that employs tris(2,4,6‐trifluorophenyl)borane was reached. Mixtures of this borane with 1,4‐diazabicyclo[2.2.2]octane (DABCO) exhibited excellent catalytic activity for the hydrogenation of alkylidene malonates. In fact, this transformation could be achieved under milder conditions than those we reported previously. Moreover, the reaction scope could be expanded to other electron deficient olefins containing esters, sulfones or nitro functionalities as electron‐withdrawing substituents.     

Nucleophilicities and Nucleofugalities of Thio- and Selenoethers

Rate constants for the reactions of dialkyl chalcogenides with laser flash photolytically generated benzhydrylium ions have been measured photometrically to integrate them into the comprehensive benzhydrylium-based nucleophilicity scale. Combining these rate constants with the previously reported equilibrium constants for the same reactions provided the corresponding Marcus intrinsic barriers and made it possible to quantify the leaving group abilities (nucleofugalities) of dialkyl sulfides and dimethyl selenide. Due to the low intrinsic barriers, dialkyl chalcogenides are fairly strong nucleophiles (comparable to pyridine and N-methylimidazole) as well as good nucleofuges; this makes them useful group-transfer reagents.     

Computational Insights on Periodicity in Bonding and Lewis Acidity and Basicity of the p-Block Trispyrazolylborate Complexes

Hydrotris(pyrazolyl)borate ligands are a popular class of ligands to stabilize both Lewis acidic and Lewis basic main group compounds. In this work we analyze the low-valent group 13–15 compounds of hydrotris(3,5-dimethyl-pyrazolyl)borate ligand, [Tp*E]^x, 1–15 (E=group 13 element, x=0; E=group 14 element, x=1+ ; E=group 15 element, x=2+) based on density functional theory. A periodic increment in intrinsic Lewis acidity is observed down the group due to increased E−N bond polarization towards nitrogen, resulting in lower energy secondary binding sites. However, global Lewis acidity measures in terms of FIA and IIA indicate the dependency on the choice of the nucleophile. In general, this study underscores the potential of the Tp* ligand in stabilizing the reactive low-valent p-block elements.     

Perfluoropentaphenylborole: A New Approach to Lewis Acidic,Electron‐Deficient Compounds

Zirconocene is the key : A new synthetic method, which utilizes zirconocene‐mediated coupling of alkynes, has been developed for the preparation of a new class of highly Lewis acidic boroles (see scheme). Such compounds hold potential for applications in catalysis and the field of electron‐deficient organic materials.

     

Lewis acidity/basicity of pi-electron systems: theoretical study of a molecular interaction between a pi system and a Lewis acid/base

Molecular interactions between pi systems having different pi-electron character (benzene, hexafluorobenzene, and borazine), and a Lewis acid/base (borane and ammonia) were theoretically studied. An attractive interaction between benzene, the electron-rich pi system, and borane was observed. On the other hand, repulsive interactions between benzene and ammonia was observed when the lone pair of nitrogen points toward the benzene ring. In contrast, an attractive interaction between hexafluorobenzene, an electron-deficient pi system, and ammonia was observed. Unexpectedly, a weak attractive interaction between hexafluorobenzene and borane was also observed. Borazine shows an interaction both to borane and ammonia. The attraction between the nitrogen atom of borazine and borane was larger than that between the boron atom of borazine and ammonia.     

氟离子亲合能——定量标度Lewis酸性强度的方法

评述了Lewis酸碱电子理论及氟离子亲合能的概念,指出了可以通过离子回旋共振实验方法和量子化学理论方法获得氟离子亲合能数值以定量确定Lewis酸性强度,并介绍了表示Lewis酸性强度的PF-标度。     

A Highly Lewis Acidic Strontium ansa-Arene Complex for Lewis Acid Catalysis and Isobutylene Polymerization

The potential of a dicationic strontium ansa-arene complex for Lewis acid catalysis has been explored. The key to its synthesis was a simple salt metathesis from SrI₂ and 2 Ag[Al(OR^F)₄], giving the base-free strontium-perfluoroalkoxyaluminate Sr[Al(OR^F)₄]₂ (OR^F=OC(CF₃)₃). Addition of an ansa-arene yielded the highly Lewis acidic, dicationic strontium ansa-arene complex. In preliminary experiments, the complex was successfully applied as a catalyst in CO₂-reduction to CH₄ and a surprisingly controlled isobutylene polymerization reaction.     

基于路易斯结构式的含氧酸酸性半定量判定方法:1/2规则

基于经典价键理论中路易斯结构式建立了判定常见含氧酸酸性强弱的半定量方法“1/2规则”,并利用密度泛函理论验证了方法的可靠性和可行性。该方法可以用于判定常见含氧酸的强弱,同时解释多元酸的逐级电离过程、同种元素不同价态含氧酸酸性强弱变化规律等。该方法有助于学生掌握各类含氧酸酸性的判定规律,改变现有机械记忆的学习方法,引导学生形成“结构-能量-性质”的化学学科基本逻辑体系,提升学生的“宏观辨识与微观探析”化学学科核心素养。     

Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Lewis Acid/Base Reactions with Triorganylboranes

Reaction of the donor‐stabilized silylene 1 (which is three‐coordinate in the solid state and four‐coordinate in solution) with BEt₃ and BPh₃ leads to the formation of the Lewis acid/base complexes 2 and 3 , respectively, which are the first five‐coordinate silicon compounds with an Si?B bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies.     

The Affinity of Some Lewis Bases for Hexafluoroisopropanol as a Reference Lewis Acid: An ITC/DFT Study

To figure out the possible role of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as well as to provide reference thermochemical data in solution, the formation of Lewis acid-base complexes between HFIP (Lewis acid) and a series of 8 different Lewis bases (3 sulfoxides, 3 Nsp² pyridine derivatives, 1 aromatic amine, 1 cyclic aliphatic ether) was examined by isothermal titration calorimetry (ITC) experiments and static density functional theory augmented with Dispersion (DFT−D) calculations. Measured ITC association enthalpy values (ΔH_a) lie between −9.3 and −14 kcal mol⁻¹. Computations including a PCM implicit solvation model produced similar exothermicity of association of all studied systems compared to the ITC data with ΔH_a values ranging from −8.5 to −12.7 kcal mol⁻¹. An additional set of calculations combining implicit and explicit solvation by chlorobenzene of the reactants, pointed out the relatively low interference of the solvent with the HFIP-base complexation: its main effect is to slightly enhance the Gibbs energy of the HFIP-Lewis base association. It is speculated that the interactions of bulk HFIP with Lewis bases therefore may significantly intervene in catalytic processes not only via the dynamic microstructuring of the medium but also more explicitly by affecting bonds’ polarization at the Lewis bases.     

Lewis Acid Behavior of SF4: Synthesis,Characterization, and Computational Study of Adducts of SF4 with Pyridine and Pyridine Derivatives

Sulfur tetrafluoride was shown to act as a Lewis acid towards organic nitrogen bases, such as pyridine, 2,6‐dimethylpyridine, 4‐methylpyridine, and 4‐dimethylaminopyridine. The SF₄?NC₅H₅, SF₄?2,6‐NC₅H₃(CH₃)₂, SF₄?4‐NC₅H₄(CH₃), and SF₄?4‐NC₅H₄N(CH₃)₂ adducts can be isolated as solids that are stable below ?45 °C. The Lewis acid–base adducts were characterized by low‐temperature Raman spectroscopy and the vibrational bands were fully assigned with the aid of density functional theory (DFT) calculations. The electronic structures obtained from the DFT calculations were analyzed by the quantum theory of atoms in molecules (QTAIM). The crystal structures of SF₄?NC₅H₅, SF₄?4‐NC₅H₄(CH₃), and SF₄?4‐NC₅H₄N(CH₃)₂ revealed weak S?N dative bonds with nitrogen coordinating in the equatorial position of SF₄. Based on the QTAIM analysis, the non‐bonded valence shell charge concentration on sulfur, which represents the lone pair, is only slightly distorted by the weak dative S?N bond. No evidence for adducts between quinoline or isoquinoline with SF₄ was found by low‐temperature Raman spectroscopy.     

On the Lewis Basicity of Phosphoramides: A Critical Examination of Their Donor Number through Comparison of Enthalpies of Adduct Formation with SbCl5 and BF3

The Lewis basicity of a series of phosphoryl compounds was examined using DFT and ab initio methods, including solvation effects. The enthalpies of adduct formation with two archetypal Lewis acids, antimony pentachloride and boron trifluoride, used to define the donor number DN and the BF₃ affinity (BF₃A) respectively, were examined. The BF₃ adducts allow the use of the high-accuracy G4 approach, whereas for SbCl₅ adducts, three different DFT formalisms, including empirical dispersion corrections, were used because the G4 formalism is not available for third-row elements. For a comparison with experimental data, solvation effects were taken into account by using the polarizable continuum model. The experimental BF₃ affinities were well reproduced by G4 calculations when including PCM solvation. Conversely, comparisons of our calculated values and experimental results reported in the literature show that SbCl₅ enthalpies for phosphoramides are in error. In particular the DN for HMPA should be revised.     

Cover Picture: Trimeric Perfluoro‐ortho‐phenylenemercury: A Versatile Lewis Acidic Host (Chem. Eur. J. 21/2003)

The cover picture shows how trimeric perfluoro‐ortho‐phenylene mercury (center), one of the simplest trifunctional Lewis acidic hosts, interacts with organic molecules to afford various adducts. The planarity of this trinuclear complex as well as its overall polarizability compounded with relativistic effects at mercury permits the occurrence of noncovalent interactions and accounts for the tendency of this compound to form cofacial dimers as observed in the structure of the acetone adduct (top left). With a triply coordinated acetone molecule, the structure of this adduct also substantiates the cooperative effects that arise from the proximity and accessibility of the mercury centers. The complexation of arenes, such as benzene (bottom left) and naphthalene (bottom right), also occurs and leads to the formation of binary stacks in which the arene establishes multiple linkages with the mercury centers of the trifunctional Lewis acids. In addition to displaying unusual coordination environment, the arene units present in those stacks exhibit remarkable phosphorescent properties. For more details, see the paper by F. P. Gabbaï, R. E. Taylor, and M. R. Haneline on p. 5188 ff.