Quantification of Ion‐Pairing Effects on the Nucleophilic Reactivities of Benzoyl‐ and Phenyl‐Substituted Carbanions in Dimethylsulfoxide

Second‐order rate constants for the reactions of acceptor‐substituted phenacyl (PhCO?CH^??Acc) and benzyl anions (Ph?CH^??Acc) with diarylcarbenium ions and quinone methides (reference electrophiles) have been determined in dimethylsulfoxide (DMSO) solution at 20 °C. By studying the kinetics in the presence of variable concentrations of potassium, sodium and lithium salts (up to 10^?2 mol L^?1), the influence of ion‐pairing on the reaction rates was examined. As the concentration of K⁺ did not have any influence on the rate constants at carbanion concentrations in the range of 10^?4–10^?3 mol L^?1, the acquired rate constants could be assigned to the reactivities of the free carbanions. The counter ion effects increase, however, in the series K⁺<Na⁺<Li⁺, and the sensitivity of the carbanion reactivities toward variation of the counter ion strongly depends on the structure of the carbanions. The reactivity parameters N and s_N of the free carbanions were derived from the linear plots of log k₂ against the electrophilicity parameters E of the reference electrophiles, according to the linear‐free energy relationship log k₂(20 °C)=s_N(N+E). These reactivity parameters can be used to predict absolute rate constants for the reactions of these carbanions with other electrophiles of known E parameters.     

Anionic polymerization with alkaline earth counterions—I. Propagation kinetics of living poly-2-vinylpyridine

Propagation kinetics of the homopolymerization of 2-vinylpyridine initiated with cumyl barium and with difunctional dimeric 1,1-diphenylethyl barium in tetrahydrofuran (THF) are reported. Conductance studies on the monofunctional living polymer solution, at concentrations from 10^?3 to 10^?5 M over the range 15 to ?70°C, revealed the presence of triple ions in thermodynamic equilibrium with free ions and ion pairs. The dissociation constant of ion pairs decreases from 1 × 10^?11 M at 15°C to 0.7 × 10^?11 M at ?70°C with an enthalpy of dissociation of 2.5 kJ/mol. Comparison with the analogous system of monofunctional polystyryl barium led to the conclusion that the living polymer of 2-vinylpyridine is 10 times less dissociated. Occurrence of intramolecular complexation, as observed with sodium and magnesium cations, thus appears much less pronounced in the presence of the barium cation on account of its relatively large radius. Kinetic studies showed that living poly-2-vinylpyridine, irrespective of its functionality, propagates essentially via ion pairs. The corresponding constant of propagation ranges from 294 M^?1 sec^?1 at 22°C to 20.7 M^?1 sec^?1 at ?50°C with an activation energy of 20 kJ/mol. The polymers contain more than 50%, isotactic triads.     

Electroconductivity study of active centers of polar vinyl monomers in the anionic polymerization

Ion equilibria in THF solutions of organolithium compounds are studied at ?30°C. The extremely low values of the dissociation constants (from 10^?11 to 10^?13M) and the formation of ion triples of the types A^?, B⁺, A^? prove that active centers exist in THF mainly as contact ion pairs with very small interionic distance (～ 2.5 Å) and tend to form higher associates. A comparison is made between the physicochemical characteristics of active centers of vinyl nitriles, ketones, and esters. A planar structure is proposed for the anion of methyl methacrylate. The results indicate that the intramolecular chelate complexation between the polar group and the counterion of the active center decreases in the order . A greater participation of ion triples in the propagation reaction is proposed.     

Kinetics of Anionic Polymerization of ε-Caprolactone (εCL). Propagation of Poly-ε=CL-K+ Ion Pairs

Kinetics of the anionic polymerization of ε-caprolactone (εCL) initiated with (CH₃)₃SiO^?K⁺ and carried out in THF solution has been studied in the temperature range from 0 to 20°C by using a calorimetric method. From the kinetic results and from conductometric measurements of the dissociation constant of the living Poly-εCL^?K⁺ ion pairs (K_D ²⁰ ? (4 ± 2) × 10^?10 mol/L), we concluded that at the conditions indicated above and for concentrations of active centers ranging from 10^?3 to 3.7 × 10^?2 mol/L, propagation proceeds on the ion pairs and is disturbed neither by dissociation nor by the formation of higher aggregates. For the polymerization of εCL proceeding on the poly-εCL^?K⁺     

Anionic polymerization with alkaline earth counterions—II Propagation kinetics of living poly-4-vinylpyridine

4-Vinylpyridine was polymerized by cumyl barium in THF at 0°C. Detailed conductance studies at various concentrations of the living oligomer solution gave similar experimental results as for 2-vinylpyridine, i.e. triple ions exist in thermodynamic equilibrium with free ions and ion pairs. The dissociation constant of ion pairs increases from 1.96 × 10^?10 M at 15°C to 4.35 × 10^?10 M at ?70°C with enthapy and entropy of dissociation of ?3.9 kJ/mol and ?200 J mol^?1 K^?1 respectively. The extent of dissociation of ion pairs of living oligo-4-vinylpyridine is comparable to that of living polystyrene ($\text{K}{}_1\text{? 10}{}^{\mathrm{?10}}$) but higher than that of living poly-2-vinylpyridine ($\text{K}{}_1\text{? 10}{}^{\mathrm{?11}}$). This result is interpreted in terms of intramolecular complexation which is no longer favourable when the nitrogen atom is situated at the 4-position of the pyridine nucleus. Studies of propagation kinetics revealed that 4-vinylpyridine polymerizes by the same reaction mechanism as the 2-isomer, the active sites being essentially ion pairs. At 0°C, its propagation constant was found to be 211.1 M^?1 sec^?1 compared with 151.04 M^?1 sec^?1 for living poly-2-vinylpyridine. As for free radical polymerization, the polymers contain only about 26% isotactic triads.     

Polybromostryl macromers and their anionic polymerization

The decomposition of polybromostyryl carbanions (PBS^?), obtained by anionic polymerization of 4-bromostyrene in tetrahydrofuran (THF), was investigated in the dark in a temperature range of ?6–?21°C. It was accompanied by the evolution of bromine anions and by the formation of polymeric allylic carbanions (λ_max = 575 nm; ε_max = 6800 eq^?1·L·cm^?1). The reaction mechanism was elucidated. The rate constant of the unimolecular rate-determining step of the process was 1.3 × 10^?5 s^?1 and 9.7 × 10^?5 s^?1 at ?21 and ?6°C, respectively. Its apparent energy of activation E_app = 18.38 Kcal/mol. The polybromostyrenes with allylic carbanions at their ends may decompose further. Their “dark” decomposition yielded 1,3-butadiene-1,3-diphenyl-macromers. The mechanisms of decomposition of the PBS^? carbanions and the dark decomposition of the polybromostyryl allylic carbanions are analogous. The rate constant of the latter process was 2.5 × 10^?6 s^?1 at ?6°C. The anionic polymerization of prepared macromers can be initiated in THF at ?78°C by α-methylstyryl carbanions, which do not react, however, with PBS^? carbanions. “Comblike” polymacromers were prepared in which each branch had a molecular weight of about 50,000. The overall molecular weight of the polymacromer was estimated to be about 1 × 10⁶. It has been assumed that the 2–1 mode of addition to the diene group of the macromer is predominant during its polymerization. The 3–4 mode of addition followed by proton shift represents the termination step. The 4–3 mode of addition was ruled out on the basis of spectroscopic evidence.     

The influence of polar solvents on ions and ion pairs in the anionic polymerization of styrene

In the rather polar organic solvents dimethoxyethane, tetrahydrofuran and 3-methyltetrahydrofuran, the behaviour of contact ion pairs, solvent-separated ion pairs and free carbanions of polystyryl sodium has been investigated by kinetic and conductivity measurements. Both the equilibrium between the two kinds of ion pairs and the dissociation of solvent-separated ion pairs to free anions are followed over a wide range of temperature. Thereby, conditions can be found under which the polymerization takes place almost exclusively via one of the two types of ion pairs.The thermodynamic parameters of the equilibria and the Arrhenius parameters of the propagation rate constants of the different kinds of propagating chain ends are reported. The equilibria between these species are strongly influenced by the solvent whereas the individual propagation rate constants are scarcely affected by the solvent. The “effective charge distance” in the solvent-separated ion pair can be estimated from the corresponding dissociation constant. The mobility of the polymer carbanion is discussed.     

Measurement of the association constants through micro-Raman spectra of supersaturated lithium perchlorate droplets

High quality micro-Raman spectra of the LiClO4droplet with mass of nanogram scale were obtained at various concentrations from dilute to supersaturated state.From component band analysis of the v1-ClO4band,four peaks at 933.3,936.8,942.1 and950.7 cm 1were identified and assigned to free solvated perchlorate anion,solvent-shared ion pair,contact ion pair and complex ion aggregates,respectively.As expected,the signature of free solvated ClO4ion was observed to decrease in intensity with the increase in concentration.The intensity of the signature from solvent-shared ion pair was observed to rise with increase in concentration from 1.8 mol/kg to 5.0 mol/kg before decreasing as the concentration was further increased to 5.6mol/kg.Signatures of contact ion pair and of complex ion aggregates were shown to increase as the concentration was enhanced.Based upon the Eigen mechanism,we show that three association equilibria can be used to describe the transformations between free solvated perchlorate anion,solvent-shared ion pair,contact ion pair and complex ion aggregates.The overall association constant,K,and the stepwise association constants Ki(i=1 to 3)in the Eigen mechanism were determined separately with values of 0.025±0.003,0.023±0.002,0.068±0.033 and 0.686±0.174.Based on these constants,the electronic performance can be reasonably predicted by the optimum choice of electrolyte concentrations.     

Electric conductivity of polybutadienyl- and polyisoprenyl-lithium in tetrahydrofurane and dimethoxyethane

The electric conductivity of polybutadienyl-lithium and polyisoprenyl-lithium has been investigated in tetrahydrofuran and dimethoxyethane solutions over wide temperature and concentration ranges (0 to ?70°; 7·10^?2 to 1·10^?7 and 5·10^?3 to 1·10^?7 mol/l). Dissociation constants, enthalpy and entropy of dissociation of ion pairs, relative constants for formation of ion triplets, and interionic distances were calculated for each system investigated. The nature of “living” chains under these conditions is considered.     

Ion equilibria in THF solutions of models of “living” methacrylonitrile oligomers with Li+ counterion

The electro-chemical characteristics of isobutyronitrile lithium (P₁Li) and 2-lithio-4-cyano-2,4-dimethylpentanenitrile (P₂Li) are studied. The dissociation constants K of P₁Li and P₂Li are of the order of 10^?11M and show that in THF mainly contact ion pairs exist. The lower value of K for P²Li is an indication for intramolecular complexation between the counterion and the cyano group, next to the active center. Both compounds tend to form ion triples. The results obtained show that in THF the nitrile group of the second monomer unit participates both in intra- and intermolecular interactions with the counterion.     

Etude de la reactivite de la vinyl-2 Pyridine en polymerisation anionique—I: Cinetique de l'homopolymerisation AVEC les contre-ions Na+ et Cs+ Dans le tetrahydrofuranne

A kinetic study of the anionic polymerization of 2VP in T.H.F. solution has shown that, for Na⁺ as counter-ion, experimental results can be interpreted by the existence of thermodynamic equilibrium between three types of active centres (contact ions pairs, free ions and positive triple ions) the reactivities of which were estimated. When the counter-ion is Cs⁺, the system can be described by a single equilibrium between ion pairs and free ions. The reactivity of free anions has been measured at various temperatures; at 0°, for example the rate constant of propagation k_(?) = 105.000 l mole^?1 sec^?1.     

The stereoregularity of polystyrenes obtained by different ion pairs of polystyryl alkali salts

The stereoregularity of polystyrenes obtained with sodium, potassium, rubidium, and cesium naphthalenes in various solvents was determined by ¹³C-NMR spectroscopy. Polystyrenes produced by contact ion pairs of polystyryl cesium in dioxane and tetrahydrofuran (THF) had the proportions of a 57–58% racemic dyad (P_r), whereas the P_r values increased to 65 and 69% by solvating Cs⁺ counterions in dimethoxyethane and by agent-separating them with crown ether, respectively. Polystyrene obtained by contact ion pairs of polystyryl sodium in dioxane showed a P_r of 66%; polymers produced by solvent-separated ion pairs of polystyryl sodium in THF at ?78°C had a P_r of 71%. A polymerization system which contained alkali counterions with large ionic radii and solvents with low dielectric constants in which only contact ion pairs existed produced polystyrenes with isotactic-rich configurations. The stereoregularity of polystyrene produced by contact ion pairs of polystyryl potassium and rubidium in tetrahydropyran (THP) occurred intermediately between that of polymers obtained in diethyl ether and THF. It was concluded that the stereoregulation of contact ion pairs may be closely related to the interionic distance of the ion pair.     

Polymérisation anionique des diènes. III. Etude thermodynamique de la propagation du butadiène et de i'isoprène par les organo-alcalins

The present work is concerned with the influence of the polymerization temperature on the propagation mechanisms of polyisoprenyl- and polybutadienyl-alkali metals. The thermodynamic parameters of the contact ion pairs and free ions propagations have been calculated. With Li⁺ in dioxane solvent, the vinyl propagation is stereospecific (for isoprene, the propagation is mainly 4–3). In comparison with benzene, the vinyl propagation of the polydienyl-Li contact ions pairs should be due to complexation of Li⁺ by dioxane, an electron donor having a weak dielectric constant. In general, the stereospecificity of the propagation of contact ion pairs decreases with increasing counterion size; little difference has been observed with K⁺ and Cs⁺ ion pairs in dioxane and benzene media. For isoprene, the methyl substituant should have chiefly a steric effect in the propagation of free ions, whereas it should confer a polar character to the isoprene molecule in the presence of ions pairs.     

Anionic polymerization and copolymerization of p-bromostyrene

Monodispersed poly(4-bromostyrenes) (PBs) and their block copolymers with styrene, isoprene, and 3-methylbutene were prepared and characterized by GPC and NMR. Polystyryl and α-methylstyryl carbanions act as effective initiators of the anionic polymerization of Bs in THF. The undersirable side reactions, due to thermally or photochemically induced decomposition of the bromostyryl carbanions, PBs^?, may be eliminated by conducting the reaction at ?78°C and in the dark. Under such conditions, the rate constant of propagation, k_p (?78°), is 1.5 × 10³ M^?1 s^?1. Radical anions, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Bs}^{\mathop - \limits_ \cdot} $\end{document}, formed as result of electron transfer from sodium naphthalenide to Bs, may eject spontaneously bromine ions. This step and reactions involving the respective phenyl radicals compete at ?78°C with the addition steps leading to polymer formation. Electron affinity of Bs seems to be much higher than that of styrene or isoprene, and PBs^? carbanions do not add to the latter monomers. Addition of Bs to polyisoprenyl carbanions leads to formation of the BsIBs block copolymers. BsIBs, prepared in THF, may be converted by preferential hydrogenation of the 1–2 adducts into block copolymers of Bs with poly(2-methylbutene) and isoprenyl segments. The effectiveness of Bs as a flame retarding constituent of polymeric systems seems to be much more pronounced when it is incorporated in a “block” than in a random fashion. A considerably larger fraction of PBs is required to achieve the same LOI value when the respective homopolymers are blended. Spatial distribution of the easily charred microdomains in the block copolymers is believed to be responsible for this phenomenon.     

State in solution, structure, and regioselectivity of reactions of the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative

According to the spectrophotometric data, the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative in diethyl ether exists as contact ion pairs, while in THF, according to the spectrophotometric and¹³C NMR data, solvent-separated ion pairs are predominantly formed. According to the¹³C NMR data, the carbanion in the solventseparated ion pairs has a structure close to the propargylic type. The regioselectivity of reactions of the lithium derivative with ethyl halides in diethyl ether, THF, and hexamethyphosphoramide, with benzyl chloride in the first two solvents, and with methanol in THF were studied. The protonation with methanol proceeds exclusively at the allenylic center (C-1) while the ethylation and especially benzylation proceed predominantly at the propargylic center (C-3). The selectivity of ethylation of the propargylic center of both solvent-separated ion pairs in THF and contact ion pairs in diethyl ether increases as the hardness of the ethylating agent increases, and in the case of the same ethyl halide, the selectivity increases from the solvent-separated ion pairs to the contact ion pairs. The spectral data obtained and the data on changes in the regioselectivity do not allow one to believe that the contact ion pairs of the lithium derivative in ether exhibit the intramolecular coordination of the lithium cation to the methoxy group, which might lead to the allenylic structure of contact ion pairs of this derivative. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2043–2051, November, 1997.     

Mixed activation and mixed inhibition of the oxidoreductase activity of Rhus vernicifera laccase by different Pd~(2 ) ion concentration

Kinetic experiments were performed to study the effects of Pd2 ion on the oxidation of 5,6-dibro-mo-2,3-dicyanohydroquinone catalyzed by Rhus vernicifera laccase under condition of pH 4.5 and 30 × 0. 1℃ . The results showed that the mixed activation could be observed when Pd2 ion was at low concentrations. The competitive and non-competitive activation constants were 9 × 10 and 2 × 10-6 mol/L, respectively. With the increase of Pd2 ion concentration, the activation was gradually converted into mixed inhibition, and the competitive and non-competitive inhibition constants were 6 × 10-6 and 32 × 10-6 mol/L, respectively.     

Trityl salt—initiated polymerization of α-methylstyrene

The initiation reaction of the polymerization of α-methylstyrene by trityl tetrachloroferate and tritylhexachloroantimonate in 1,2-dichloroethane at 20°C was studied. The rate constants were 14 × 10^?3 and 27 × 10^?3 L mol^?1s^?1, respectively. The dissociation constants of tritylterachloroferate (K_d = 0.88 × 10^?4M^?1) and tritylhexachloroantimonate (K_d = 2.64 × 10^?4M^?1) was determined. The effect of electron acceptors and donors on the dissociation equilibrium and initiation rate was investigated. It was shown that in strongly dissociated ion pairs such as stable carbenium salts the electron donors and acceptors have no appreciable effect on the magnitude of the dissociation. The temperature dependence of the rate constants in the ?20–+20°C range yielded the following thermodynamic parameters for trityltetrachloroferate: E_i = 8.54 kcal/mol; A = 3.2 × 10⁴ mol^?1s^?1; ΔH* = 8 kcal/mol; and S* = ?39.8 eu.     

Radiation-Induced Polymerization of Urea Canal Complex. Part 4. Radiation-Induced Polymerization of Acrylonitrile in Urea-Ethylene Glycol Supercooled Liquid System

Abstract

Using elementary analysis, NMR on ^{3 1}P and ¹H nuclei, and electroconductivity methods, the acrylonitrile, methacrylonitrile, formaldehyde, and β-propiolactone anionic polymerization in the presence of triethylphosphine is shown to follow the macrozwitterion mechanism: quartary phosphonium being on one end of a polymer chain and the growing anion on the other. The number of covalent bonds through the whole polymer chain between charges forming the active center increases with the propagation reaction. The active centers stationary concentration in the system is low when connected with both the slow initiation reaction and with the fast active centers termination reaction. Thus the ion interaction of different growing polymer chains can be ignored. The active centers parts occurring in the form of ion pairs (the ends are near and form the “cyclic”) and of free ions (the ends are separated) are determined by the monomolecular equilibrium, and its constant depends upon the macro-zwitterion polymerization degree K_d ⁽ⁿ⁾ = K_d ^(I)n^3/2. Such constant depends upon the chain length affords the macrozwitterion self-accelerated propagation with its length, as the free ion reactivity is more than that of ion pairs. The self-accelerated chain propagation effect shows up as an increase of polymerization initial rate order and polymer molecular weight in the monomer concentration. This effect can be avoided by the introduction of electrolyte into the system, which dissociates into ions and transforms all cyclic ion pairs into the linear form, the latter dissociating independently of chain length. The strict mathematical analysis of stationary and nonstationary polymerization kinetics made it possible to determine all the elementary constants separately: K_i = 5.6 × 10^?4 liters/ (mole) (min); K_- = 2.5 × 10⁴ liter/ (mole) (min); K_± = 2.0 liters/ (mole) (min); K_t = 0.84/min; K_t ¹ = 4/min; K_d ^(I) = 10^?4; K₃ = 0.07 × 10^?4 mole/liter.     

Conductivity studies on living polymers with an α-oxide terminal unit in tetrahydrofuran

The dissociation constants were determined in tetrahydrofuran for “living” polymers, built of a polystyrene block and statistically one terminal unit of ethylene oxide, butylene oxide or styrene oxide using lithium, sodium and potassium as counterions. The values for the dissociation constants at 25° of the alcoholate ion pairs are of the order of 10^?9–10^?10 M. It was found that living polymers with a terminal unit of styrene oxide and a lithium or sodium counterion form ion triplets at concentrations of about 10^?5 M. Their dissociation constants, calculated by the Fuoss and Kraus method, are of the order of 10^?5 M.     

Polymerization of Cyclosiloxanes. I. Kinetic Studies on Living Polymer—Octamethylcyclotetrasiloxane Systems

The kinetics of the anionic polymerization of octamethylcyclotetrasiloxane (D₄) initiated by α-methylstyrene living polymer in tetrahydrofuran was studied. The following kinetic scheme was postulated: Initiation: Propagation: where S^- and M represent the initiator and D₄, respectively. At a living end concentration of 0.0377 mole/l. and a monomer concentration of 1.5 mole/l. in tetrahydrofuran at 25°C. the following kinetic data were obtained: k₁ = 2.3 × 10^?4 l./mole-sec., k₂ < 2.3 × 10^?5 sec.^?1, k₃ = 2.75 × 10^?2l./mole-sec. k₄ ≈ 1.17 × 10^?2 sec.^?1, K₁ > 10 l./mole and K₂ ≈ 2.35 l./mole. The rate constants k₁ and k₃ were found to be dependent on the concentration of anions. This is attributed to the dissociation of ion pairs to free ions at lower concentration. Under the experimental conditions studied the majority of the anions were present in the form of ion pairs. The reactivity of the free ions is about 100 times greater than that of ion pairs. There is no temperature effect on K₂, indicating zero ΔH and positive ΔS in the propagation reaction.