MALDI‐TOF‐MS analysis of living cationic polymerization of vinyl ethers. III. Polymerization with SnCl4 and TiCl4 in the absence of additives

Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis revealed that the precision control (or the living nature) of the cationic polymerization of vinyl ethers with SnCl₄ or TiCl₄ critically depends on the Lewis acid concentration and temperature. Specifically, at an extremely low Lewis acid concentration, for example, the polymerization with the HCl–vinyl ether adduct (an initiator) is living at ?78 °C in CH₂Cl₂ solvent, whereas side reactions occurred at a higher concentration of SnCl₄ or at a higher temperature, ?15 °C. This was more pronounced with SnCl₄ than with TiCl₄, which was due to a stronger Lewis acidity of SnCl₄ as suggested by NMR analysis of the model reactions. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1258–1267, 2001     

Catalyse par les acides de Lewis—I : Etude cinetique de la reaction d'esterification des olefines catalysee par SnCl4

Lewis acids, such as SnCl₄, TiCl₄, FeCl₃ AlCl₃ and ZnCl₂ catalyze the esterification of olefins in CH₃CO₂H or CH₃CH₂CO₂H. SnCl₄ reacts with carboxylic acids to give the acid complex SnCl₄.2(RCO₂H), which raises the level of acidity. The following relation applies: log k_ex = αH_o + β (α≠?1), activation energy (7·5 kcal/mole) and activation entropy (?28 cal/M°K). Solvent isotope effects are measured (k_H/k_D>1). The mechanism implies a slow proton transfer.     

Relationship Between the J(Sn–C–H) of the Dimethyltin Dichloride Adducts of some Pyridines and Anilines,and the Donor Strength of the Lewis Bases

A study by titrimetric methods of the donor strength of pyridine and aniline and some of their para -substituted derivatives, and the J (¹¹⁹Sn–C–H) of their adducts with dimethyltin dichloride in nitrobenzene, has shown that the p K _b of a Lewis base and its para -substituted derivatives varies linearly with the J (¹¹⁹Sn–C–H) of the adducts of dimethyltin dichloride (Me₂SnCl₂), with the Lewis base dissolved in an inert solvent. A graphical plot of the p K _b of a given series of Lewis bases versus the J (Sn–C–H) of their complexes with Me₂SnCl₂ in nitrobenzene (at the same temperature, and same complex concentration) gives a straight line with a negative gradient, making possible the deduction of the other parameter (e.g. p K _b) for a Lewis base in the series, where the one parameter (e.g. J (Sn–C–H) is known. The graph for each series of Lewis base has its own characteristic gradient, and the gradients appear proportional in magnitude to the donor strengths of each class of the bases, making it possible to deduce from such graphs which series of Lewis bases are the stronger donors.     

Demetallation of α,β,γ,δ-tetrakis(p-sulfophenyl) porphiniron(III) in mineral acid–alcohol–water media

Demetallation rates of α,β,γ,δ-tetrakis(p-sulfophenyl)porphiniron(III) in hydrochloric acid–ethanol–water, perchloric acid–ethanol–water, and sulfuric acid–alcohol–water media were determined. For a given acidity value H₀ the order of the rates for the three acids was HCl > H₂SO₄ > HClO₄. This is also the order for complex formation between acid anion and iron(III). Consequently ligands as well as protons are involved in the breaking of bonds between the metal and the porphyrin leading to the formation of the activated complex. The log k values for HCl and HClO₄ media were not linearly related to the Hammett acidity function as they were for sulfuric acid–ethanol–water media. The average ΔH? and ΔS?values for the HCl media were 18.4 ± 1.4 kcal/mol and ? 19 ± 3 cal K mol, respectively, in very close agreement with those for H₂SO₄ media despite the difference in H ₀ dependence. For H₂SO₄–alcohol–water media the order of the rates was butanol > propanol > ethanol with little difference between isomeric alcohols.     

A Frustrated Phosphane–Borane Lewis Pair and Hydrogen: A Kinetics Study

The energy profile of a frustrated Lewis pair (FLP) dihydrogen splitting system was determined by a combined experimental kinetic and DFT study. A trimethylene‐bridged phosphane–borane FLP was converted into its endothermic H₂‐cleavage product by sequential H⁺/H^? addition. The system could be handled at low temperature, and the kinetics of the H₂ elimination were determined to give a rate constant of k_HH,exp(299 K)=(2.87±0.1)×10^?4 s^?1 in solution. The primary kinetic isotope effects were determined; for example, (k_HH/k_DD)_exp=3.19. The system was accurately analyzed by DFT calculations.     

Demetallation of α, β, γ, δ-tetra(p-sulfophenyl)porphineiron(III) in sulfuric acid-ethanol-water media

The rate of demetallation of α, β, γ,δ-tetra(p-sulfophenyl)porphineiron (III), Fe(TPPS)^3-, was determined in sulfuric acid-ethanol-water media for 8.5-10.65M sulfuric acid at different temperatures. The overall reaction was the conversion of the complex Fe(TPPS)^3- into the diacid species H₄TPPS^2- without other spectrophotometrically important species being formed to an appreciable extent, as shown by three isosbestic points at 418, 462, and 563 nm. The rate was first order in the Fe(TPPS)^3- concentration. The pseudo-first-order rate constants k were exponentially dependent on the sulfuric acid concentration, and log k was linearly dependent on the Hammett acidity function –H₀. The average ΔH? and ΔS? values for five reaction media were 18.4 ± 1.4 kcal/mol and 19 ± 3 cal/°K · mol, respectively. The linear relationship between log k and (-H₀) and the approximately constant values of ΔH? ΔS? over the acid range investigated indicated that the same mechanism of demetallation was operative over this acid range. Because of the dependence of the pseudo-first-order rate constants on the acidity of the medium, the mechanism probably involves the addition of protons to pyrrole N atoms to assist in the breaking of iron (III)-nitrogen bonds.     

Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics

Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework Al_FR Lewis acid sites are often found in their H‐forms. The formation of Al_FR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of Al_FR Lewis sites in dehydrated zeolites and their precursors—“perturbed” Al_FR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)₃AlOH groups and are characterized by a broad ²⁷Al NMR resonance (δ_i=59–62 ppm, C_Q=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the ²⁷Al MAS NMR spectrum. Dehydroxylation of (SiO)₃AlOH occurs at mild temperatures and leads to the formation of Al_FR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)₃Al Lewis sites exhibit an extremely broad ²⁷Al NMR resonance (δ_i≈67 ppm, C_Q≈20 MHz, and η≈0.1).     

Lewis Superacidic Ionic Liquids with Tricoordinate Borenium Cations

The first examples of ionic liquids based on borenium cations, [BCl₂L]⁺, are reported. These compounds form highly Lewis acidic liquids under solvent‐free conditions. Their acidity was quantified by determining the Gutmann acceptor number (AN). Extremely high ANs were recorded (up to AN=182, δ_31P=120 ppm), demonstrating that these borenium ionic liquids are the strongest Lewis superacids reported to date, with the acidity enhanced by the ionic liquid environment.     

Ru–η6‐Arene Cations [{(Ph2PC6H4)2B(η6‐Ph)}RuX]+ (X=Cl,H) as Lewis Acids

The reactivity of [{(Ph₂PC₆H₄)₂B(η⁶‐Ph)}RuCl][B(C₆F₅)₄] ( 1 ) as a Lewis acid was investigated. Treatment of 1 with mono and multidentate phosphorus Lewis bases afforded the Lewis acid–base adducts with the ortho‐carbon atom of the coordinated arene ring. Similar reactivity was observed upon treatment with N‐heterocyclic carbenes; however, adduct formation occurred at both ortho‐ and para‐carbon atoms of the bound arene with the para‐position being favoured by increased steric demands. Interestingly treatment with isocyanides resulted in adduct formation with the B‐centre of the ligand framework. The hydride‐cation [{(Ph₂PC₆H₄)₂B(η⁶‐Ph)}RuH] [B(C₆F₅)₄] was prepared via reaction of 1 with silane. This species in the presence of a bulky phosphine behaves as a frustrated Lewis pair (FLP) to activate H₂ between the phosphorus centre and the ortho‐carbon atom of the η⁶‐arene ring.     

Synthesis and solid‐state structures of t‐Bu3Ga–EPh3 Lewis acid–base adducts

Three Lewis acid–base adducts t‐Bu₃Ga–EPh₃ (E = P 1 , As 2 , Sb 3 ) were synthesized by reactions of Ph₃E and t‐Bu₃Ga and characterized by heteronuclear NMR (¹H, ¹³C (³¹P)) and IR spectroscopy, elemental analysis and single crystal X‐ray diffraction. Their structural parameters are discussed and compared to similar t‐Bu₃Ga adducts. The strength of the donor‐acceptor interactions within 1 – 3 was investigated in solution by temperature‐dependent ¹H NMR spectroscopy and by quantum chemical calculations.     

Reaction of an “Invisible” Frustrated N/B Lewis Pair with Dihydrogen

D ‐(+)‐Camphor forms the enamine 2 with piperidine. Compound 2 adds HB(C₆F₅)₂ at the enamine carbon atom C3 to form a Lewis acid/Lewis base adduct (exo‐/endo‐isomers of 3 ). Exposure of 3 to dihydrogen (2.5 bar, room temperature) leads to heterolytic splitting of H₂ to form the H⁺/H^? addition products ( 4 , two diastereoisomers) of the “invisible” frustrated Lewis pairs ( 5 , two diastereoisomers) that were apparently generated in situ by enamine hydroboration under equilibrium conditions.     

The Strongest Acid: Protonation of Carbon Dioxide

The strongest carborane acid, H(CHB₁₁F₁₁), protonates CO₂ while traditional mixed Lewis/Brønsted superacids do not. The product is deduced from IR spectroscopy and calculation to be the proton disolvate, H(CO₂)₂⁺. The carborane acid H(CHB₁₁F₁₁) is therefore the strongest known acid. The failure of traditional mixed superacids to protonate weak bases such as CO₂ can be traced to a competition between the proton and the Lewis acid for the added base. The high protic acidity promised by large absolute values of the Hammett acidity function (H₀) is not realized in practice because the basicity of an added base is suppressed by Lewis acid/base adduct formation.     

Zero‐, one‐ and two‐dimensional hydrogen‐bonded structures in the 1:1 proton‐transfer compounds of 4,5‐dichlorophthalic acid with the monocyclic heteroaromatic Lewis bases 2‐aminopyrimidine,nicotinamide and isonicotinamide

The structures of the anhydrous 1:1 proton‐transfer compounds of 4,5‐dichlorophthalic acid (DCPA) with the monocyclic heteroaromatic Lewis bases 2‐aminopyrimidine, 3‐(aminocarbonyl)pyridine (nicotinamide) and 4‐(aminocarbonyl)pyridine (isonicotinamide), namely 2‐aminopyrimidinium 2‐carboxy‐4,5‐dichlorobenzoate, C₄H₆N₃⁺·C₈H₃Cl₂O₄⁻, (I), 3‐(aminocarbonyl)pyridinium 2‐carboxy‐4,5‐dichlorobenzoate, C₆H₇N₂O⁺·C₈H₃Cl₂O₄⁻, (II), and the unusual salt adduct 4‐(aminocarbonyl)pyridinium 2‐carboxy‐4,5‐dichlorobenzoate–methyl 2‐carboxy‐4,5‐dichlorobenzoate (1/1), C₆H₇N₂O⁺·C₈H₃Cl₂O₄⁻·C₉H₆Cl₂O₄, (III), have been determined at 130 K. Compound (I) forms discrete centrosymmetric hydrogen‐bonded cyclic bis(cation–anion) units having both R₂²(8) and R₁²(4) N—H...O interactions. In (II), the primary N—H...O‐linked cation–anion units are extended into a two‐dimensional sheet structure via amide–carboxyl and amide–carbonyl N—H...O interactions. The structure of (III) reveals the presence of an unusual and unexpected self‐synthesized methyl monoester of the acid as an adduct molecule, giving one‐dimensional hydrogen‐bonded chains. In all three structures, the hydrogen phthalate anions are essentially planar with short intramolecular carboxyl–carboxylate O—H...O hydrogen bonds [O...O = 2.393 (8)–2.410 (2) Å]. This work provides examples of low‐dimensional 1:1 hydrogen‐bonded DCPA structure types, and includes the first example of a discrete cyclic `heterotetramer.' This low dimensionality in the structures of the 1:1 aromatic Lewis base salts of the parent acid is generally associated with the planar DCPA anion species.     

Carbon-13 NMR spectroscopy of acrylic monomer and Lewis acid complexes

¹³C NMR spectra of acrylic monomers complexed with a Lewis acid were measured and their electronic structures discussed in relation to their alternating copolymerizability. The β-carbon of acrylonitrile and methacrylonitrile showed a downfield shift due to the complex formation with the Lewis acid, while the α-carbon showed an upfield shift and the nitrile carbon showed no significant shift. The degree of shift of olefinic carbons decreased in the following order: AlCl₃ > EtAlCl₂ > Et_1.5AlCl_1.5 > Et₂AlCl > SnCl₄, EtOAlCl₂ > Et(EtO)AlCl, which seems to run parallel to the Lewis acidity and acid strength. On the other hand, the chemical shift of olefinic carbons of methyl acrylate, methyl methacrylate, and olefinic diesters was influenced little by complex formation with Lewis acids, whereas the carbonyl and alkoxyl carbons were deshielded significantly by the complex formation. These results are discussed in terms of electron distribution on the carbons and an alternating polymerization mechanism.     

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 Coupled Electron Transfer of Metal–Oxygen Intermediates

Redox‐inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal–oxygen intermediates, such as metal–oxo and metal–peroxo complexes. The mechanisms of the oxidative C?H bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)–oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)₃ have been unified as rate‐determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)₃) by iron(III)–oxo complexes. All logarithms of the observed second‐order rate constants of Lewis acid‐promoted oxidative C?H bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)–oxo complexes exhibit remarkably unified correlations with the driving forces of proton‐coupled electron transfer (PCET) and metal ion‐coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)₃ to the metal–oxo moiety has been confirmed for Mn^IV–oxo complexes. The enhancement of the electron‐transfer reactivity of metal–oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox‐inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)–peroxo complexes, resulting in acceleration of the electron‐transfer reduction but deceleration of the electron‐transfer oxidation. Such a control on the reactivity of metal–oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca²⁺ in the oxidation of water to dioxygen by the oxygen‐evolving complex in photosystem II.     

Pushing the Lewis Acidity Boundaries of Boron Compounds With Non‐Planar Triarylboranes Derived from Triptycenes

Bending the planar trigonal boron center of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR spectroscopy and X‐ray diffraction of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis base revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf₂N^? anion illustrates the unrivaled Lewis acidity of these species. Increasing the pyramidalization of the boron center and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed access to new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.     

Controlled Generation of 9‐Boratriptycene by Lewis Adduct Dissociation: Accessing a Non‐Planar Triarylborane

A highly bent triarylborane, 9‐boratriptycene, was generated in solution by selective protodeboronation of the corresponding tetra‐aryl boron ate complex with the strong Brønsted acid HNTf₂. The iptycene core confers enhanced Lewis acidity to 9‐boratriptycene, making it unique in terms of structure and reactivity. We studied the stereoelectronic properties of 9‐boratriptycene by quantifying its association with small N‐ and O‐centered Lewis bases, as well as with sterically hindered phosphines. The resultant Lewis adducts exhibited unique structural, spectroscopic, and photophysical properties. Beyond the high pyramidalization of the 9‐boratriptycene scaffold and its low reorganization energy upon Lewis base coordination, quantum chemical calculations revealed that the absence of π donation from the triptycene aryl rings to the boron vacant p_z orbital is one of the main reasons for its high Lewis acidity.     

Hydro­gen bonding in proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases

The crystal structures of quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate trihydrate, C₉H₈N⁺·C₇H₅O₆S⁻·3H₂O, (I), 8‐hydroxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate monohydrate, C₉H₈NO⁺·C₇H₅O₆S⁻·H₂O, (II), 8‐amino­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate dihydrate, C₉H₉N₂⁺·C₇H₅O₆S⁻·2H₂O, (III), and 2‐carboxy­quinolinium 3‐carboxy‐4‐hydroxy­benzene­sulfonate quinolinium‐2‐carboxylate, C₁₀H₈NO₂⁺·C₇H₅O₆S⁻·C₁₀H₇NO₂, (IV), four proton‐transfer compounds of 5‐sulfosalicylic acid with bicyclic heteroaromatic Lewis bases, reveal in each the presence of variously hydrogen‐bonded polymers. In only one of these compounds, viz. (II), is the protonated quinolinium group involved in a direct primary N⁺—H⋯O(sulfonate) hydrogen‐bonding interaction, while in the other hydrates, viz. (I) and (III), the water mol­ecules participate in the primary intermediate interaction. The quinaldic acid (quinoline‐2‐carboxylic acid) adduct, (IV), exhibits cation–cation and anion–adduct hydrogen bonding but no direct formal heteromolecular interaction other than a number of weak cation–anion and cation–adduct π–π stacking associations. In all other compounds, secondary interactions give rise to network polymer structures.     

Controlled Cationic Polymerization of 1‐Methoxy‐1,3‐Butadiene: Long‐Lived Species‐Mediated Reaction and Control over Microstructure with Weak Lewis Bases

Controlled cationic polymerization of trans‐1‐methoxy‐1,3‐butadiene was achieved through the design of appropriate initiating systems, yielding soluble polymers with controllable molecular weights. The combined use of SnCl₄ or GaCl₃ as a Lewis acid catalyst and a weak Lewis base in conjunction with HCl as a protonogen resulted in efficient and controlled polymerization. The M_n values of the product polymers increased linearly along the theoretical line, which indicates that intermolecular crosslinking reactions negligibly occurred. In addition, the polymer microstructure was critically dependent on the weak Lewis base employed. In particular, the use of tetrahydrofuran as an additive resulted in the highest 4,1/4,3‐structure ratio (96/4). Weak Lewis bases also affected the polymerization rates but exhibited unique trends that differed from their effects on the cationic polymerization of alkyl vinyl ethers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 288–296