Copolymerization of carbon dioxide and propylene oxide using an aluminum porphyrin system and its components

The catalytic activities of tetraphenylporphinatoaluminum chloride (TPPAlCl) and its propylene oxide adduct (TPPAl(PO)₂Cl) were investigated in detail together with a quarternary salt Et₄NBr for the copolymerization of carbon dioxide and propylene oxide. In addition, for the components and starting raw materials of the catalyst systems, catalytic activities were examined for the copolymerization. The TPPAlCl catalyst delivered oligomers containing ether linkages to a large extent, regardless of its PO adduction. And cyclic propylene carbonate, as byproduct, was formed in a very small portion. Using the TPPAlCl coupled with Et₄NBr as a catalyst system, the formation of ether linkages was reduced significantly in the copolymerization; however, the obtained oligomer still contained ether linkages of 25.0 mol % in the backbone. On the other hand, the formation of cyclic carbonate was increased to 22.4 mol % relative to the oligomer product. The results indicate that the salt, which was coupled with the TPPAlCl catalyst, plays a key role in reducing the formation of ether linkage in the oligomer and, however, in enhancing the formation of cyclic carbonate. Similar results were obtained for the copolymerization catalyzed by the TPPAl(PO)₂Cl/Et₄NBr system. That is, the formation of ether linkages was not restricted further by the PO adduction of the TPPAlCl component in the catalyst system. Only oligomers with a relatively high molecular weight were produced. This indicates that the PO adduction of the TPPAlCl component contributes highly to the initiation and propagation step in the oligomerization, consequently leading to a relatively high molecular weight oligomer. In contrast, the Et₄NBr, as well as the Et₂AlCl, produced only cyclic carbonate in a very low yield. Furthermore, tetraphenylporphine exhibited no catalytic activity, regardless of using together with Et₄NBr. On the other hand, the Et₂AlCl coupled with Et₄NBr provided a low molecular weight oligomer having ether linkages of 92.3 mol % in addition to the cyclic carbonate. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3329–3336, 1999     

Biodegradable Polycarbonate Synthesis by Copolymerization of Carbon Dioxide with Epoxides Using a Heterogeneous Zinc Complex

As a means for the chemical fixation of carbon dioxide and the synthesis of biodegradable polycarbonates, copolymerizations of carbon dioxide with various epoxides such as cyclohexene oxide (CHO), cyclopetene oxide, 4-vinyl-1-cyclohexene-1,2epoxide, phenyl glycidyl ether, allyl glycidyl ether, propylene oxide, butene oxide, hexene oxide, octene oxide, and 1-chloro-2,3-epoxypropane were investigated in the presence of a double metal cyanide catalyst (DMC). The DMC catalyst was prepared by reacting K₃Co(CN)₆ with ZnCl₂, together with tertiary butyl alcohol and poly(tetramethylene ether glycol) as complexing reagents and was characterized by various spectroscopic methods. The DMC catalyst showed high activity (526.2 g-polymer/g-Zn atom) for CHO/CO₂ (P_CO2 = 140 psi) copolymerization at 80 °C, to yield biodegradable aliphatic polycarbonates of narrow polydispersity (M_w/M_n = 1.67) and moderate molecular weight (M_n = 8900). The DMC catalyst also showed high activities with different CO₂ reactivities for other epoxides to yield various aliphatic polycarbonates with narrow polydispersity.     

Phosphasalen Indium Complexes Showing High Rates and Isoselectivities in rac‐Lactide Polymerizations

Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal‐catalyzed ring‐opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac ‐lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m ⁻¹ min⁻¹, THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (P _i=0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives.     

l‐Methioninium chloride and l‐seleno­methioninium chloride at 103 K

The crystal structures of the title compounds, (S)‐1‐carboxy‐3‐(methyl­sulfanyl)­propanaminium chloride, C₅H₁₂NO₂S⁺·Cl⁻, and (S)‐1‐carboxy‐3‐(methyl­selanyl)­propanaminium chloride, C₅H₁₂NO₂Se⁺·Cl⁻, are isomorphous. The proton­ated l ‐methionine and l ‐seleno­methionine mol­ecules have almost identical conformations and create very similar contacts with the Cl⁻ anions in the crystal structures of both compounds. The amino acid cations and the Cl⁻ anions are linked viaN—H⋯Cl⁻ and O—H⋯Cl⁻ hydrogen bonds.     

The kinetics of anion equilibration of human erythrocytes in phosphate-containing media of low chloride concentration

The pH-equilibration of human erythrocytes is accompanied by the transport of permeating anions. The kinetics of adaptation of erythrocytes to various outside solutions was investigated by continuous registration of extracellular pH and Cl⁻- and K⁺-concentration. In phosphate buffered solutions of low Cl⁻-content, the equilibration process consists of at least two components:

• •exchange of Cl⁻ for OH⁻ or HCO₃⁻;
• •exchange of Cl⁻ for phosphate

.The obtained time-dependence of extracellular pH and Cl⁻-concentration was fitted by means of a regression model which consists of two exponential terms assuming a fast and a slow transport component. By increasing of phosphate buffer concentration the fast time constant of Cl⁻- and pH-kinetics and the slow time constant of Cl⁻-kinetics were decreased whereas the slow pH-time constant was enhanced. CO₂-supply of the suspension tends to increase the slow time constant of pH- and Cl⁻-kinetics. These results can be explained by suggesting that the transport system is inhibited by phosphate or influenced by transmembrane potential.     

New rhodium(I) water‐soluble complexes with 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phospha‐adamantane iodides and their catalytic activity

The water‐soluble phosphine ligands, 1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane (tpa) and 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane iodides (Rtpa⁺I⁻), with alkyl=methyl(mtpa⁺I⁻), ethyl (etpa⁺I⁻) and n‐propyl, (ptpa⁺I⁻), and mtpa⁺Cl⁻ react with [Rh₂Cl₂(CO)₄] giving the rhodium(I) complexes [RhCl(CO)(tpa)₂], [RhI(CO)(Rtpa⁺I⁻)₂], [RhCl‐­(CO)(mtpa⁺Cl⁻)₃] and [RhI(CO)(Rtpa⁺I⁻)₃]. The properties and reactivities of the complexes have been investigated using ¹H and ³¹PNMR and IR spectroscopies. The five‐coordinate complexes in solutions show dynamic properties. The complexes are catalysts of the water‐gas shift reaction, the hydrogenation of CC and CO bonds, the hydroformylation of alkenes and the isomerization of unsaturated compounds. Copyright © 1999 John Wiley & Sons, Ltd.     

Reduction of Phosphine Oxide by Using Chlorination Reagents and Dihydrogen: DFT Mechanistic Insights

Extensive DFT calculations provide detailed mechanistic insights into the metal-free reduction of phosphine oxide Ph₃P=O by using chlorination reagents O=CClX (X=COCl, Cl, OCCl₃ and Ph) and H₂. Fast electrophilic attack to the P=O group oxygen atom is favored by exergonic CO₂ release to form phosphonium Ph₃PCl⁺ and chloride Cl⁻, which may slowly cleave H₂ by an unstable HPh₃PCl complex yielding Ph₃PH⁺ and Cl⁻ ions in solution. Moderate heating is required to accelerate the slow H₂-activation step and to eliminate HCl to form phosphine Ph₃P instead of Ph₃PH⁺Cl⁻ salt as the desired product. Though partially quenched by Ph₃P (and reactant Ph₃P=O if present), borane B(2,6-F₂C₆H₃)₃ can be still combined with Cl⁻ and Ph₃P as reactive frustrated Lewis pair (FLP) catalysts.     

Boosting Electroreduction of CO2 over Cationic Covalent Organic Frameworks: Hydrogen Bonding Effects of Halogen Ions

We present the first example of charged imidazolium functionalized porphyrin-based covalent organic framework (Co-iBFBim-COF-X) for electrocatalytic CO₂ reduction reaction, where the free anions (e.g., F⁻, Cl⁻, Br⁻, and I⁻) of imidazolium ions nearby the active Co sites can stabilize the key intermediate *COOH and inhibit hydrogen evolution reaction. Thus, Co-iBFBim-COF-X exhibits higher activity than the neutral Co-BFBim-COF, following the trend of F⁻<Cl⁻<Br⁻<I⁻. Particularly, the Co-iBFBim-COF-I⁻ showed nearly 100 % CO₂ selectivity at a low full-cell voltage of 2.3 V, and achieved a high CO₂ partial current density of 52 mA cm⁻² with a turnover frequency of 3018 h⁻¹ at 2.4 V in the anion membrane electrode assembly, which is 3.57 times larger than that of neutral Co-BFBim-COF. This work provides new insight into the importance of free anions in the stabilization of intermediates and decreasing the local binding energy of H₂O with active moiety to enhance CO₂ reduction reaction.     

Alternating copolymerization of propylene oxide and carbon dioxide with highly efficient and selective (salen)Co(III) catalysts: Effect of ligand and cocatalyst variation

Synthetic routes to a series of new (salen)CoX (salen = N,N′-bis(salicylidene)-1,2-diaminoalkane; X = Br or pentafluorobenzoate (OBzF₅)) species are described. Several of these complexes are active for the copolymerization of propylene oxide (PO) and CO₂, yielding regioregular poly(propylene carbonate) (PPC) without the generation of propylene carbonate byproduct. Variation of the salen ligand, as well as the inclusion of organic-based ionic or Lewis basic cocatalysts, has dramatic effects on the resultant (salen) CoX catalytic activity. Highly active (R,R)-(salen- 1 )CoOBzF₅ (salen- 1 = N,N′-bis(3,5- di-tert-butylsalicylidene)-1,2-diaminocyclohexane) catalysts with [Ph₄P]Cl or [PPN]Y ([PPN] = bis(triphenylphosphine)iminium; Y = Cl or OBzF₅) cocatalysts exhibited turnover frequencies up to 720 h⁻¹ for rac-PO/CO₂ copolymerization, yielding PPC with greater than 90% head-to-tail connectivity. Additionally, the (R,R)-(salen- 1 )CoOBzF₅/[PPN]Cl catalyst system demonstrated a k_rel of 9.7 for the enchainment of (S)- over (R)-PO when the copolymerization was carried out at low temperatures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5182–5191, 2006     

Gas-phase ion equilibria studies of protons and chloride ions in propanol and acetone

The gas-phase clustering reactions of proton in propanol and acetone, and chloride ions in acetone were investigated. The −ΔH_n−1,n values obtained for clustering reactions (n−1,n) were as follows: H⁺ (C₃H₇OH)_n−1 + C₃H₇OH ⇄ H⁺ (C₃H₇OH)_n, (2, 3) 18.9 kcal mol⁻¹, (3, 4) 14.2 kcal mol⁻¹, (4, 5) 11.7 kcal mol⁻¹; H⁺ (CH₃COCH₃)₂ + CH₃COCH₃ ⇄ H⁺ (CH₃COCH₃)₃, 14.2 kcal mol⁻¹; and Cl⁻ + CH₃COCH₃ ⇄ Cl⁻ (CH₃COCH₃), 12.4 kcal mol.⁻¹. For clustering reactions, Cl⁻ (CH₃COCH_3n−1 + CH₃COCH₃ ⇄ Cl⁻ (CH₃COCH₃)_n where n ≥ 2, the equilibria could not be established; probably due to the isomerization of ligand acetone molecules from the keto to enol form.     

Are Two Metal Ions Better than One? Mono- and Binuclear α-Diimine-Re(CO)3 Complexes with Proton-Responsive Ligands in CO2 Reduction Catalysis

Here, the reduction chemistry of mono- and binuclear α-diimine-Re(CO)₃ complexes with proton responsive ligands and their application in the electrochemically-driven CO₂ reduction catalysis are presented. The work was aimed to investigate the impact of 1) two metal ions in close proximity and 2) an internal proton source on catalysis. Therefore, three different Re complexes, a binuclear one with a central phenol unit, 3 , and two mononuclear, one having a central phenol unit, 1 , and one with a methoxy unit, 2 , were utilised. All complexes are active in the CO₂-to-CO conversion and CO is always the major product. The catalytic rate constant k_cat for all three complexes is much higher and the overpotential is lower in DMF/water mixtures than in pure DMF (DMF=N,N-dimethylformamide). Cyclic voltammetry (CV) studies in the absence of substrate revealed that this is due to an accelerated chloride ion loss after initial reduction in DMF/water mixtures in comparison to pure DMF. Chloride ion loss is necessary for subsequent CO₂ binding and this step is around ten times faster in the presence of water [ 2 : k^Cl(DMF)≈1.7 s⁻¹; k^Cl(DMF/H₂O)≈20 s⁻¹]. The binuclear complex 3 with a proton responsive phenol unit is more active than the mononuclear complexes. In the presence of water, the observed rate constant k_obs for 3 is four times higher than of 2 , in the absence of water even ten times. Thus, the two metal centres are beneficial for catalysis. Lastly, the investigation showed that the phenol unit has no impact on the rate of the catalysis, it even slows down the CO₂-to-CO conversion. This is due to an unproductive, competitive side reaction: After initial reduction, 1 and 3 loose either Cl⁻ or undergo a reductive OH deprotonation forming a phenolate unit. The phenolate could bind to the metal centre blocking the sixth coordination site for CO₂ activation. In DMF, O−H bond breaking and Cl⁻ ion loss have similar rate constants [ 1 : k^Cl(DMF)≈2 s⁻¹, k^OH≈1.5 s⁻¹], in water/DMF Cl⁻ loss is much faster. Thus, the effect on the catalytic rate is more pronounced in DMF. However, the acidic protons lower the overpotential of the catalysis by about 150 mV.     

A one‐step strategy for aliphatic poly(carbonate‐ester)s with high performance derived from CO2, propylene oxide and l‐lactide

To improve the performance of PPC, aliphatic poly(carbonate‐ester)s were prepared in one‐step strategy from the terpolymerization of CO₂, propylene oxide (PO), and l ‐lactide (L ‐LA) catalyzed by zinc glutarate. Consequently giving high‐molecular weight terpolymers (PPCLAs) in a very high yield (8450.8–9435.8 g mol^?1 of Zn). The resulting terpolymers PPCLAs were characterized by ¹H NMR, showing that PPCLAs had an almost alternating structure for the components of CO₂, PO, and L‐LA. The influence of molecular weight and L‐LA content on the properties of PPCLAs was also investigated. Differential scanning calorimetry and thermogravimetric analysis (measurements revealed that the glass transition temperature (T _g) and thermal decomposition temperature (T _d) of PPCLAs are all much higher than those of PPC and increased with increasing molecular weight and L‐LA content. Tensile tests showed that the high mechanical properties of PPCLAs are due to the introduction of L‐LA into the copolymerization of CO₂ and PO. Furthermore, PPCLA4 exhibits high degradability, and after 10 weeks, the weight loss increases up to 6.58%, which is significantly higher than that of PPC of 4.58%. Copyright © 2016 John Wiley & Sons, Ltd.     

Three-body association of CO+ and N2. The case for a chemical bond

Hamilton, Bierbaum and Leone recently reported a very efficient vibrational quenching of CO⁺ (v) by N₂, only about six collisions being required for quenching at 300 K. This is an exceedingly efficient quenching process in the light of recent systematic studies of diatomic molecular ion vibrational quenching. To probe further the CO⁺−N₂ interaction, the rate coefficient for three-body association of CO⁺ and N₂ with He as third body was measured and is very large, being 2.1 × 10⁻²⁹ cm⁶ s⁻¹ at 298 K and 1.8 × 10⁻²⁸ cm⁶ s⁻¹ at 80 K. Both the efficient quenching and the rapid association imply a strong interaction between CO⁺ and N₂, much stronger than the expected ≈ 0.2 eV electrostatic potential well depth. These experiments indicate a “chemical bonding” interaction between CO⁺ and N₂, with a well depth as large as 1 eV.     

Anion Cryptates: Synthesis,Crystal Structures,and Complexation Constants of Fluoride and Chloride Inclusion Complexes of Polyammonium Macrobicyclic Ligands

Three macrobicyclic octamines 1–3 and the macrotricyclic hexadecamine 14 have been synthesized. The octamines 1–3 bind anionic substrates when protonated. The stability constants of the complexes between the protonated forms of the macrobicyclic polyamines and halide anions have been determined by pH-metric measurements. The stability constants in H₂O are very high; 1 in its hexaprotonated form binds F⁻ with high selectivity (selectivity F⁻/Cl⁻ > 10⁸), while 3 exhibits strong stability constants for both F⁻ and Cl⁻. Three X-ray structures have been obtained, one where F⁻ is held inside the cavity of 1 · 6H⁺, one where Cl⁻ is included in 3 · 6H⁺, and 3 · 6H⁺ where the cavity is empty.     

High yield synthesis of biodegradable poly(propylene carbonate) from carbon dioxide and propylene oxide

A novel SalenCo^III (2,4‐dinitrophenoxy) (Salen = N,N'‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamino) and 1,10‐phenanthroline monohydrate catalyst system was designed and employed for the copolymerization of CO₂ and propylene oxide (PO). The perfectly alternating copolymerization of CO₂ and PO proceeds effectively under middle temperature and pressure to yield poly(propylene carbonate) with a high yield and a high number average molecular weight of polymer. The structure of polymer was characterized by the IR and NMR measurements. The perfectly alternating copolymer was confirmed. The MALDI‐TOF spectrum insinuates that the copolymerization of CO₂ and PO was initiated by H₂O. Copyright © 2016 John Wiley & Sons, Ltd.     

Cooperative photoproduction of Xe2+Cl− in liquid Cl2/Xe solutions: Stimulated emission and gain measurements

Cooperative photogeneration of Xe₂⁺Cl⁻ can be accomplished by near UV laser excitation of Cl₂/Xe solutions with a high quantum efficiency. Gain measurements on the Xe₂⁺Cl⁻ (4²Γ) transition are reported. The liquid phase rare gas halides should be regarded as a family of ideal “dye” lasers.     

Reactions of CF2 carbene with Br2, Cl2 and H2 studied by means of CO2 laser photolysis and infrared diode laser spectroscopy

Reactions of CF₂ carbene, generated by infrared CO₂ laser photolysis of CHClF₂, with Br₂, Cl₂ and H₂ were investigated using infrared diode laser spectroscopy. Absolute rate constants at about 550 K for the reactions with Br₂ and Cl₂ were found to be (2.7 ± 0.9) × 10⁻¹⁵and (3.5 ± 1.3) × 10⁻¹⁵ cm³ molecule⁻¹ s⁻¹, respectively. No reaction was observed with H₂.     

Transport of hydrochloric acid through anion-exchange membrane NEOSEPTA-AFN: Application of Nernst–Planck equation

The paper deals with the determination of mobility of H₃O⁺ and Cl⁻ ions on the basis of experiments with hydrochloric acid carried out in a batch mixed cell with an anion-exchange membrane NEOSEPTA-AFN, which have been completed by measurements of the membrane conductivity. The dependencies of mobility of H₃O⁺ and Cl⁻ ions upon the acid concentration in the membrane have been approximated by the second degree polynomial, whose coefficients have been determined with the help of a model based on the Nernst–Planck equation — the membrane being modeled as a homogeneous gel phase containing fixed positive charges, water molecules and mobile H₃O⁺ and Cl⁻ ions. Using all the experimental data obtained at various acid concentrations and rotational speeds of the stirrers, it has been found that mobility of H₃O⁺ and Cl⁻ ions is strongly affected by the acid concentration in the membrane.     

2,2′‐(Iminodimethylene)bis(1H‐benzimidazolium)(1+) chloride

The title compound, C₁₆H₁₆N₅⁺·Cl⁻ (nbbH⁺·Cl⁻), displays N—H⋯N, N—H⋯Cl and π–π inter­actions in the crystal packing. The Cl⁻ anion is chelated by the nbbH⁺ cation via two N—H⋯Cl hydrogen bonds. Inter‐ion N—H⋯N and N—H⋯Cl hydrogen bonds link ions related by 2₁ screw axes into chains along the c axis. These chains are further linked by glide‐plane operations to generate a three‐dimensional network, which is additionally stabilized by inter­chain π–π inter­actions.     

A structural study of Si6‐ring‐containing [Si6Cl14]2− chlorosilicates

The crystal structures of four substituted‐ammonium dichloride dodecachlorohexasilanes are presented. Each is crystallized with a different cation and one of the structures contains a benzene solvent molecule: bis(tetraethylammonium) dichloride dodecachlorohexasilane, 2C₈H₂₀N⁺·2Cl⁻·Cl₁₂Si₆, (I), tetrabutylammonium tributylmethylammonium dichloride dodecachlorohexasilane, C₁₆H₃₆N⁺·C₁₃H₃₀N⁺·2Cl⁻·Cl₁₂Si₆, (II), bis(tetrabutylammonium) dichloride dodecachlorohexasilane benzene disolvate, 2C₁₆H₃₆N⁺·2Cl⁻·Cl₁₂Si₆·2C₆H₆, (III), and bis(benzyltriphenylphosphonium) dichloride dodecachlorohexasilane, 2C₂₅H₂₂P⁺·2Cl⁻·Cl₁₂Si₆, (IV). In all four structures, the dodecachlorohexasilane ring is located on a crystallographic centre of inversion. The geometry of the dichloride dodecachlorohexasilanes in the different structures is almost the same, irrespective of the cocrystallized cation and solvent. However, the crystal structure of the parent dodecachlorohexasilane molecule shows that this molecule adopts a chair conformation. In (IV), the P atom and the benzyl group of the cation are disordered over two sites, with a site‐occupation factor of 0.560 (5) for the major‐occupied site.