Significant Induction Period Research Articles

Water vapor effect on the physico-geometrical reaction pathway and kinetics of the multistep thermal dehydration of calcium chloride dihydrate.

This study investigated how water vapor influences the reaction pathway and kinetics of the multistep thermal dehydration of inorganic hydrates, focusing on CaCl2·2H2O (CC-DH) transforming into its anhydride (CC-AH) via an intermediate of its monohydrate (CC-MH). In the presence of atmospheric water vapor, the thermal dehydration of CC-DH stoichiometrically proceeded through two distinct steps, resulting in the formation of CC-AH via CC-MH under isothermal conditions and linear nonisothermal conditions at a lower heating rate (β). Irrespective of atmospheric water vapor pressure (p(H2O)), these reaction steps were kinetically characterized by a physico-geometrical consecutive process involving the surface reaction and phase boundary-controlled reaction, which was accompanied by three-dimensional shrinkage of the reaction interface. In addition, a significant induction period was observed for the second reaction step, that is, the thermal dehydration of CC-MH intermediate to form CC-AH. With increasing p(H2O), a systematic increase in the apparent Arrhenius parameters was observed for the first reaction step, that is, the thermal dehydration of CC-DH to form CC-MH, whereas the second reaction step exhibited unsystematic variations of the Arrhenius parameters. At a larger β in the presence of atmospheric water vapor, the first and second reaction steps partially overlapped; moreover, an alternative reaction step of the thermal dehydration of CC-MH to form CaCl2·0.3H2O was observed between these reaction steps. The physico-geometrical phenomena influencing the reaction pathway and kinetics of the multistep thermal dehydration were elucidated by considering the effects of atmospheric and self-generated water vapor in a geometrically constrained reaction scheme.

Toward Precision Deposition of Conductive Charge-Transfer Complex Crystals Using Nanoelectrochemistry.

The lack of understanding for precise synthesis and assembly of nano-entities remains a major challenge for nanofabrication. Electrocrystallization of a charge-transfer complex (CTC), tetrathiafulvalene bromide (TTF)Br, is studied on micro/nanoelectrodes for precision deposition of functional materials. The study reveals new insights into the entire CTC electrocrystallization process from the initial nanocluster nucleation to the final elongated crystals with hollow ends grown from the working electrode to the neighboring receiving electrode. On microelectrodes, the number of nucleation sites is reduced to one by lowering the applied overpotential or precursor concentration. Certain current-time transients exhibit significant induction periods prior to stable nucleus growth. The induction regime contains small fluctuating current spikes consistent with stochastic formation of precritical nanoclusters with lifetimes of 0.1-30s and sizes of 20-160nm. Electrochemical analyses further reveal rate, size distribution, and formation/dissipation dynamics of the nanoclusters. Crystal growth of (TTF)Br is further studied on triangular nanoelectrode patterns with thickness of 5-500nm, which shows a mass-transfer-controlled process applicable for precision deposition of functional (TTF)Br crystals. This study, for the first time, establishes CTC nanoelectrochemistry as a platform technology for precise deposition of conductive crystal assemblies spanning the source and drain electrode for sensing applications.

Understanding the Behavior of Dicalcium Ferrite (Ca2Fe2O5) in Chemical Looping Syngas Production from CH4

Previous work on calcium ferrites showed they were able to convert syngas to hydrogen via chemical looping. The mixture of iron and calcium and their oxides has different thermodynamic properties than iron oxide alone. Here, the use of methane, an abundant fuel, is investigated as the reductant in chemical looping syngas production. In contrast to syngas-fueled cycles, the looping materials became more active with cycling using methane as the fuel. When reduced by methane, the looping material often showed a significant induction period, indicating that products of reduction (in particular metallic Fe) acted as a catalyst for further reduction. The behavior in a thermogravimetric analyzer (TGA) and a fluidized bed was comparable, i.e., no degradation with cycling. The reduced C2F appeared to be easily reformed when oxidized with CO2, and there was little evidence of bulk phase segregation. The improved kinetics on cycling was likely due to the separation of metallic Fe onto the surface. Using hydrogen to partially reduce C2F promotes the catalytic pyrolysis of methane.

Synthesis of silver nanoparticles by sonogalvanic replacement on aluminium powder in sodium polyacrylate solutions

The process of the formation of silver nanoparticles (AgNPs) via the method of galvanic replacement (GR) of Ag+ with aluminum powder in sodium polyacrylate (NaPA) solutions in the ultrasonic (US) field has been studied. It was observed, that the yellow colloidal solutions of stabilized AgNPs with the absorption maximum at ∼ 410 nm were obtained under the application of US power by 20 W and frequency by 20 kHz in the wide range of AgNO3 and NaPA concentrations (0.1 – 0.5 mM and 0.5 – 5.0 g/L respectively) at 25 0C. It was shown, that the GR process under US field occurs without of the significant induction period. Using the UV–vis spectroscopy the kinetics of AgNPs formation has been studied and it was observed the first order kinetics with respect to Ag+ ions both for the nucleation and growth processes. It was found that observable rate constants of nucleation are close for the all experimental conditions but the observable rate constants of growth decreased with increasing of initial concentration of AgNO3. Based on the obtained kinetic data it was proposed a mechanism of the formation of AgNPs consisted of the following two main stages: 1) the nucleation with the formation of primary nanoclusters (AgNCs) on aluminum surface followed by their ablation from the surface of the sacrificial metal by ultrasound into bulk of solution; 2) the transformation of AgNCs in AgNPs via growth from the Al surface and / or agglomeration of AgNCs. Using TEM it was found that the size of obtained AgNPs does not exceed of 25 nm and slightly depends on the initial concentrations of precursors. High antimicrobial activity of obtained colloidal solutions against gram-negative and gram-positive bacteria as well as against fungi was observed.

Sterically rigid bismuth pincer complexes; observation of the growing polymer chain in polar monomer polymerisation.

A family of pyridine dipyrrolide bismuth complexes (Mes,PhL)MX (1-6) (M = Bi, X = O-2,6-Me-C6H3 = OXyl (1); M = Sb, X = OXyl (2); M = Bi, X = O-2,6-iPr-C6H3 = ODipp (3), O-2,6-tBu-C6H3 = OArtBu (4), OtBu (5) and OCMe2Et = OAm (6), N(SiMe3)2 = N'' (7) and CH2Ph (8)) have been prepared and investigated as initiators for the ring-opening polymerisation of lactide monomers. Bismuth lactate complexes (Mes,PhL)Bi{OC(H)(Me)C(O)OR} were prepared as models for the propagating species (R = tBu (9), Me (10), iPr (11)). The first insertion of the lactide monomer is rate limiting and the second and subsequent insertions are more rapid (kinit ≪ kLA2 < kprop), leading to a significant induction period. The sterically demanding, rigid pincer ligand affords a well-defined coordination environment at the metal centre and allows for the enchainment of two lactide monomers to be differentiated spectroscopically ((Mes,PhL)Bi{OC(H)(Me)C(O)}4OX (12-X)), with this species also implied to be the true initiator for the regime of propagation with first order kinetics. Well-controlled first order kinetic data for the polymerisation of L-, D-, rac- and meso-lactide are observed.

Effect of metal ion solubility on the oxidative assembly of metal sulfide quantum dots.

The versatility of the oxidative assembly method for the creation of 2D and 3D quantum dot (QD) architectures represents both an opportunity and a challenge as a method enabling controlled placement of chemically distinct QDs in multicomponent systems. The opportunity lies in the ability to independently tune the kinetics of the different components so that they are similar (leading to well-mixed systems) or different (enabling gradient or phase-segregated composites) using a wide range of variables; the challenge lies in understanding those variables and how their interplay affects the overall kinetics. Here, we show that the identity of the cation in the sulfide matrix (M = Cd2+ vs Zn2+) plays a large role in the kinetics of assembly of mass spectrometry QDs, attributed to differences in solubility. Time resolved dynamic light scattering is used to monitor the hydrodynamic radius, R¯h. ZnS shows an exponential growth associated with reaction-limited cluster aggregation (RLCA), whereas CdS demonstrates a significant induction period (10-75 min) followed by a growth step that cannot be distinguished between RLCA and diffusion limited cluster aggregation. These data correlate with relative solubilities of the nanoparticles, as probed by free-cation concentration. Data also confirm prior studies showing that cubic-closest-packed (ccp) lattices are kinetically slow relative to hexagonally closest-packed (hcp); using the slope of the ln R¯h vs time plot for the rate constant, the values of 0.510 s-1 and 3.92 s-1 are obtained for ccp ZnS and hcp ZnS, respectively. Thus, both the structure and the solubility are effective levers for adjusting the relative reactivity of QDs toward oxidative assembly.

Comparison of aerobic atrazine degradation with zero valent aluminum and zero valent iron

This study systematically compared the degradation of atrazine (ATR) with aerobic zero-valent aluminum (ZVAl/Air) and zero-valent iron (ZVI/Air) systems. By comparing the ATR degradation curves and rate in the ZVAl/Air and the ZVI/Air systems, a significant induction period was observed in the ZVAl/Air system, and the pseudo-first-order rate constant of ATR degradation in the second stage by ZVAl was 6.4 times faster than that by ZVI. The differences in ATR degradation patterns of the two systems stemmed from the different redox nature and electrical conductivity of aluminum (oxide) and iron (oxide). Reactive oxygen species measurement and electron spin spectra analysis indicated that more hydroxyl radical was generated through molecular oxygen activation in the ZVAl/Air system, leading to enhanced ATR degradation in the ZVAl/Air process. By analyzing the intermediates of atrazine degradation, we found that ATR underwent an oxidative dealkylation and hydroxyl-dechlorination degradation pathway, and the low toxicity cyanuric acid was the final product in both systems. However, aluminum ions released in the ZVAl/Air system exceeded the regulated standard value, which might cause environmental pollution. Finally, the pros and cons of potential environmental remediation of the ZVAl/Air and ZVI/Air processes were evaluated.

Long-Lived Intermediates in a Cooperative Two-State Folding Transition.

Biomolecular folding often occurs through a cooperative two-state reactant ↔ product transition; the term cooperative does not convey that intermediate structures are nonexistent but rather that these states are not observable by existing experimental techniques. Because of this, few intermediates have been studied and characterized. Recently, ion mobility spectrometry (IMS) measurements revealed that the oligomer polyproline-13 (Pro13, which in propanol (PrOH) favors the right-handed helical PPI structure having adjacent pyrrolidine rings in a cis configuration) folds through six sequential long-lived intermediates as it converts to the all-trans-configured PPII structure that is favored in aqueous solutions. Here, we examine the PPIPrOH → PPIIaq folding transition for a HisPro13 sequence, i.e., Pro13 having a single histidine residue added to the N-terminus. Remarkably, the IMS measurements show that, upon addition of histidine, all of the IMS peaks associated with intermediate structures disappear. Instead, HisPro13 folds via a cooperative two-state transition, delayed by a significant induction period. The induction period is temperature dependent-shifting the transition to longer times at lower temperatures. Equilibrium studies show that the HisPro13 PPIPrOH → PPIIaq transition is endothermic but favored entropically. From these clues, we propose a sequential folding mechanism and develop a model that suggests that ∼13-17 long-lived intermediates are likely responsible for the induction period. In this model, intermediates are separated by average individual activation barriers of ∼90 kJ·mol-1, and are entropically favorable.

Effect of Donors on the Activation Mechanism in Ziegler–Natta Catalysis: A Computational Study

AbstractFull quantum chemical calculations, using density functional theory (DFT), have been conducted to explain the effect of donors on the “activation mechanism” in the Ziegler–Natta (Z–N) catalyst system. In the activation mechanism, the inactive TiIVCl4 catalyst converts into the active TiIIICl2Et catalyst with the help of the AlEt3 present in the system. The donors that have been considered in this study are: ethyl benzoate (eb), two representative diether cases, a phthalate donor, and a silyl ester donor. The results indicate that eb and the diether donor cases donor have a negative effect on the barriers for the activation mechanism. However, the eb donor can be displaced from the MgCl2 surface by AlEt3, which matches experimental observations. For the phthalate, silyl ester and TiCl3–OC4H8Cl cases, the results indicate that a significant induction period would be present in Z–N systems employing such donors or having such a catalytic center, before catalysis could commence.

A generalized adsorption-phase transition model to describe adsorption rates in flexible metal organic framework RPM3-Zn.

Flexible gate-opening metal organic frameworks (GO-MOFs) expand or contract to minimize the overall free energy of the system upon accommodation of an adsorbate. The thermodynamics of the GO process are well described by a number of models, but the kinetics of the process are relatively unexplored. A flexible GO-MOF, RPM3-Zn, exhibits a significant induction period for opening by N2 and Ar at low temperatures, both above and below the GO pressure. A similar induction period is not observed for H2 or O2 at comparable pressures and temperatures, suggesting the rate of opening is strongly influenced by the gas-surface interaction rather than an external stress. The induction period leads to severe mass transfer limitations for adsorption and over-prediction of the gate-opening pressure. After review of a number of existing adsorption rate models, we find that none adequately describe the experimental rate data and similar timescales for diffusion and opening invalidate prior reaction-diffusion models. Statistically, the rate data are best described by a compressed exponential function. The resulting fitted parameters exceed the expectations for adsorption but fall within those expected for phase transition. By treating adsorption as a phase transition, we generalize the Avrami theory of phase transition kinetics to describe adsorption in both rigid and flexible hosts. The generalized theory is consistent with observed experimental trends relating to induction period, temperature, pressure, and gas-substrate interaction.

Cation-Controlled Enantioselective and Diastereoselective Synthesis of Indolines: An Autoinductive Phase-Transfer Initiated 5-endo-trig Process.

A catalytic enantioselective approach to the synthesis of indolines bearing two asymmetric centers, one of which is all-carbon and quaternary, is described. This reaction proceeds with high levels of diastereoselectivity (>20:1) and high levels of enantioselectivity (up to 99.5:0.5 er) in the presence of CsOH·H2O and a quinine-derived ammonium salt. The reaction most likely proceeds via a delocalized 2-aza-pentadienyl anion that cyclizes either by a suprafacial electrocyclic mechanism, or through a kinetically controlled 5-endo-trig Mannich process. Density functional theory calculations are used to probe these two mechanistic pathways and lead to the conclusion that a nonpericyclic mechanism is most probable. The base-catalyzed interconversion of diastereoisomeric indolines in the presence of certain quaternary ammonium catalysts is observed; this may be rationalized as a cycloreversion-cyclization process. Mechanistic investigations have demonstrated that the reaction is initiated via a Mąkosza-like interfacial process, and kinetic analysis has shown that the reaction possesses a significant induction period consistent with autoinduction. A zwitterionic quinine-derived entity generated by deprotonation of an ammonium salt with the anionic reaction product is identified as a key catalytic species and the role that protonation plays in the enantioselective process outlined. We also propose that the reaction subsequently occurs entirely within the organic phase. Consequently, the reaction may be better described as a phase-transfer-initiated rather than a phase-transfer-catalyzed process; this observation may have implications for mechanistic pathways followed by other phase-transfer-mediated reactions.

Supramolecular assembly and transfer hydrogenation catalysis with ruthenium(II) complexes of 2,6-di(1H-pyrazol-3-yl)pyridine derivatives

Two new tridentate ligands 2,6-bis(5-ethyl-1H-pyrazol-3-yl)pyridine and 2,6-bis(5-benzamido-1H-pyrazol-3-yl)pyridine, have been synthesized. These ligands have been used in a new series of six complexes of formula “RuCl2(PPh3)2(LR)·nH2O” (n=1 or 2) where LR is 2,6-bis(5-R-1H-pyrazol-3-yl)pyridine (R=Me, Et, tBu, NH2, NHC{O}tBu and NHC{O}Ph). Crystal structures of [RuCl(PPh3)2(LMe)]Cl·MeOH and [Ru(OH2)(PPh3)2(LtBu)]Cl2·4CDCl3 contain six-coordinate complex centers with trans-phosphine ligands, and show that the chloride ions can occupy the first or second coordination spheres of the complexes. The latter structure demonstrates that the chloride ions in this type of compound can be labile under ambient conditions, which is an essential pre-requisite for catalytic activity. Anion metathesis yielded [Ru(OH2)(PPh3)2(LtBu)][PF6]2, which was also crystallographically characterized. All the complexes (except air-sensitive [RuCl2(PPh3)2(LNH2)]) were screened for activity towards transfer hydrogenation of acetophenone in refluxing 2-propanol. The chloride salt catalysts are active but show a significant induction period, which may imply decomposition of the complexes during the reaction. However the activity of the PF6− salt is much higher, which shows that competition between chloride and substrate for the metal center is a significant factor in catalysis by these compounds.

Diamond crystallization from a tin–carbon system at HPHT conditions

Diamond crystallization from the tin–carbon system has been studied at 7GPa and temperatures ranging from 1600 to 1900°C with reaction times from 1 to 20h. Both diamond growth on the seed crystals and diamond spontaneous nucleation were established, providing evidence for the catalytic ability of tin. A distinctive feature of the Sn–C system is the existence of a significant induction period preceding diamond spontaneous nucleation. Temperature and kinetics are found to be the main factors governing diamond crystallization process. The minimum parameters of diamond spontaneous nucleation are determined to be 7GPa, 1700°C and 20h. The stable form of diamond growth is octahedron and it does not depend on temperature. Synthesized diamonds contain high concentrations of nitrogen impurities up to about 1600ppm.

Incipient crystallization of calcium carbonate on desalination membranes: dead-end filtration with agitation

The development of reliable criteria for determining the onset of scaling on desalination membranes is of high practical value. A novel approach to systematically investigate incipient membrane crystallization and scale-particle evolution was recently reported by this laboratory, involving modeling-relevant phenomena during membrane desalination and experiments, in well-controlled pressure cells operating in dead-end mode with no agitation. However, parallel studies have shown that flow conditions equivalent to those prevailing in real desalination membrane modules are obtained in pressure cells with agitation. Therefore, this work aims to employ the aforementioned approach to the more realistic case of membrane CaCO3 scaling in dead-end desalination with agitation. Detailed data regarding incipient CaCO3 scaling of desalination membranes were obtained, by analyzing scanning electron microscopy (SEM) images, for small bulk supersaturation ratios S = 1 to 4 and short filtration times (~30–90 min). Mean shear stresses at the membrane surface were similar to those prevailing in desalination modules. The data show that concentration polarization due to salt rejection strongly affects scale-particle growth rate, insignificantly influencing particle-number surface density. There is no evidence of a significant induction period in the nucleation and growth of scale-particles on the membrane surface. The initial CaCO3 deposit flux, in mg/(m2 min), exhibits a strong dependence on membrane surface supersaturation. Experimental data on the supersaturation-dependent scale evolution appear to significantly differ from predictions based on classical concepts of heterogeneous nucleation and growth, thus indicating that non-conventional nucleation is the dominant mechanism of the membrane-scale development.

Kinetic Modeling for Thermal Dehydration of Ferrous Oxalate Dihydrate Polymorphs: A Combined Model for Induction Period–Surface Reaction–Phase Boundary Reaction

In this study, ferrous oxalate dihydrate polymorph particles, α- and β-phases, with square bipyramidal and quadratic prismatic shapes, respectively, were synthesized. Thermal dehydration of the samples was subjected to kinetic study as a typical reaction that indicates a significant induction period and a sigmoidal mass-loss behavior. On the basis of the formal kinetic analysis of the mass-loss traces recorded under isothermal, nonisothermal, and constant transformation rate conditions and the morphological observations of the surface textures of the partially reacted sample particles, a combined kinetic model for the induction period-surface reaction-phase boundary reaction was developed. The sigmoidal mass-loss behavior after the significant induction period under isothermal conditions was satisfactorily simulated by the combined kinetic model. The kinetic parameters for the component processes of induction period, surface reaction, and phase boundary reaction were separately determined from the kinetic simulation. The differences in the kinetic behaviors of the induction period and the phase boundary reaction between α- and β-phase samples were well described by the kinetic parameters. The applicability of the combined kinetic model to practical systems was demonstrated through characterizing the physicogeometrical kinetics of the thermal dehydration of ferrous oxalate dihydrate polymorphs.

Reaction pathways over copper and cerium oxide catalysts for direct synthesis of imines from amines under aerobic conditions

Copper(II) oxide, cerium oxide, and several copper(II) oxide supported on cerium oxide catalysts are explored in the aerobic oxidative homocoupling of benzylamine to form N-benzylidenebenzylamine in DMSO at 110°C. Although both CuO and CeO2 alone are shown to catalyze the reaction, CuOCeO2 catalysts are shown to most efficiently catalyze the reaction, providing higher rates (per g Cu) due to the presence of both copper and ceria species in the reactor. Catalysts with lower copper loadings and increased ceria content reduce the product yield, as ceria domains can catalyze the decomposition of the desired product as well. The amine conversion occurs with a significant induction period, associated with the putative formation of an initial benzylimine intermediate in the case of catalysis with CeO2 alone or from slow copper solubilization in cases where supported or unsupported copper catalysts are used, followed by rapid conversion to the N-benzylidenebenzylamine product. Copper leaching studies clearly demonstrate that catalysis using copper-containing catalysts is primarily associated with turnover by soluble copper species. A series of experiments targeted at elucidating the reaction pathway suggests that copper oxide domains promote the coupling of the initial intermediate, benzylimine, with benzylamine to produce the N-benzylidenebenzylamine product (path A), with a maximum production rate of 888μmol/m2h (13.3mmol/gCuh) over the pure CuO catalyst or 22.9μmol/m2h (26.1mmol/gCuh) over the CuOCeO2 catalyst. In contrast, cerium oxide domains are suggested to primarily convert the benzylimine to benzaldehyde, followed by condensation of the benzaldehyde with benzylamine in a rapid step to yield the N-benzylidenebenzylamine product (path B), with a maximum amine production rate of 2.74μmol/m2h. Both ceria and copper(II) oxide domains promote the initial benzylimine formation at comparable rates. Although the CuOCeO2 catalyst leaches about 11% of the copper during the reaction, and these soluble copper species are largely responsible for the catalytic turnover, the recovered solid can be recycled until the copper is depleted, catalyzing the reaction with an identical rate per g Cu in a second cycle, after calcination. The copper–ceria family of catalysts offers an alternative, potentially lower cost composition for the target oxidative homocoupling reaction than previously studied precious metal catalysts, although copper leaching is a distinct drawback to the catalyst composition.

On the initial growth of atomic layer deposited TiO2 films on silicon and copper surfaces

Atomic layer deposition (ALD) of TiO2 using tetrakis(diethylamino)titanium precursor and H2O was studied on silicon and copper surfaces in order to examine differences in nucleation. Both surfaces were patterned on the same substrate to assure identical deposition conditions. Spectral ellipsometry, X-ray photoelectron spectroscopy and surface profilometry were used to probe nucleation phenomena, growth rates, and surface morphology on both surfaces. The TiO2 deposition on copper was found to exhibit a significant induction period of about 20–25 ALD cycles with no observable TiO2 during the first 10–15 cycles on the copper side; in contrast, no such inhibited growth was observed in the TiO2 deposition on silicon. This result opens up potential for selective ALD of TiO2 films on silicon-based substrates patterned with a metal without the use of a mask, a self-assembled monolayer or soft lithography which is impractical for some nanoscale semiconductor fabrication processes. After film nucleation, the TiO2 growth rate on both surfaces was found to be 0.10nm/cycle.

Effect of solubilizing agent on properties of poly(3,4-ethylenedioxythiophene) (PEDOT) electrodeposited from aqueous solution

PEDOT layers were electrodeposited from aqueous solutions in the presence of various solubilizing agents. A systematic study involving a large number of solubilizers was conducted. The six surfactants used were sodium dodecyl sulfate (SDS) and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) (both anionic), Tween 80 and Triton X-100 (both non-ionic), hexadecyltrimethylammonium p-toluenesulfonate (HDTMA) and hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate (HDHEDMA) (both cationic). Two polyelectrolytes, sodium polystyrene sulfonate (PSS) and κ-carrageenan were also used.It was found that the nature of the solubilizing agent has a drastic effect on the polymerization conditions. The anionic solubilizing agents decreased the polymerization potential and eliminated the induction period of the polymerization. As a result, PEDOT layers with longer conjugation length as well as higher conductivity and transparency were deposited. These layers were incorporated into polymer solar cell as hole transporting layers and efficiencies close to the traditional spin-coated PEDOT:PSS layers have been reported. By contrast, cationic surfactants increased the polymerization potential by 0.21V and a significant induction period was observed during the polymerization. In this case, PEDOT layers of poor quality were deposited and the efficiencies of the solar cells dropped by an order of magnitude. PEDOT layers deposited in the presence of non-ionic surfactants or without any solubilizing agent showed an intermediate performance. In addition to the strong effect of charge, the bulkiness of the solubilizing agent was also found to significantly affect the polymerization and properties of PEDOT.

Rhenium-Catalyzed Trifluoromethylation of Arenes and Heteroarenes by Hypervalent Iodine Reagents

Methyltrioxorhenium acts as a catalyst (5–10 mol %) for the direct electrophilic trifluoromethylation of various aromatic and heteroaromatic compounds using the hypervalent iodine reagent 1-(trifluoromethyl)-1,2-benziodoxol-3(1H)-one (1). The products are formed in up to 77% yield. Mixtures of regioisomers are obtained in the case of substituted and heteroaromatic substrates. The reaction, typically carried out in chloroform solvent at 70 °C, shows a significant induction period. Monitoring by EPR shows the involvement of radical species. A small kinetic deuterium isotope effect of 1.3 is observed for benzene.

Intramolecular hydroamination of unactivated alkenes with secondary alkylamines catalyzed by iridium phosphino–phenolate complexes

The phosphino–phenolate complex (κ2-{2-i-Pr2PC6H4}O)Ir(COD) (COD = η4-1,5-cyclooctadiene; 1) is shown to be an effective precatalyst for the intramolecular hydroamination of unactivated alkenes with pendant secondary alkylamines, providing either pyrrolidine or piperidine heterocycles in high isolated yields. While monitoring the progress of a selected test reaction of this type, a significant induction period (~3 h) was observed; variable-temperature 1H and 31P NMR studies (25–100 °C) under catalytically relevant conditions revealed no new metal-containing species. In an effort to develop an enantiopure variant of 1, a synthetic route to the chiral (κ2-P,O)Ir(COD) complex (7), which features a 1-aryl-2,5-dialkylphospholane structure derived from (2S,5S)-2,5-hexanediol cyclic sulfate, was developed. The structure of 7 was confirmed by use of single-crystal X-ray diffraction techniques. While 7 failed to provide enantioselectivity in the intramolecular hydroamination of unactivated alkenes with pendant secondary alkylamines, the activity of 7 was found to be comparable to that of 1.