HSAB principle applied to the time evolution of chemical reactions

Time evolution of various reactivity parameters such as electronegativity, hardness, and polarizability associated with a collision process between a proton and an X- atom/ion (X = He, Li(+), Be(2+), B(3+), C(4+)) in its ground ((1)S) and excited((1)P,(1)D,(1)F) electronic states as well as various complexions of a two-state ensemble is studied using time-dependent and excited-state density functional theory. This collision process may be considered to be a model mimicking the actual chemical reaction between an X-atom/ion and a proton to give rise to an XH(+) molecule. A favorable dynamical process is characterized by maximum hardness and minimum polarizability values according to the dynamical variants of the principles of maximum hardness and minimum polarizability. An electronic excitation or an increase in the excited-state contribution in a two-state ensemble makes the system softer and more polarizable, and the proton, being a hard acid, gradually prefers less to interact with X as has been discerned through the drop in maximum hardness value and the increase in the minimum polarizability value when the actual chemical process occurs. Among the noble gas elements, Xe is the most reactive. During the reaction: H(2) + H(+) --> H(3)(+) hardness maximizes and polarizability minimizes and H(2) is more reactive in its excited state. Regioselectivity of proton attack in the O-site of CO is clearly delineated wherein HOC(+) may eventually rearrange itself to go to the thermodynamically more stable HCO(+).     

Bead-bead interaction parameters in dissipative particle dynamics: relation to bead-size, solubility parameter, and surface tension

Dissipative particle dynamics (DPD) is a mesoscale modeling method for simulating equilibrium and dynamical properties of polymers in solution. The basic idea has been around for several decades in the form of bead-spring models. A few years ago, Groot and Warren established an important link between DPD and the Flory-Huggins chi-parameter theory for polymer solutions. We revisit the Groot-Warren theory and investigate the DPD interaction parameters as a function of bead size. In particular, we show a consistent scheme of computing the interfacial tension in a segregated binary mixture. Results for three systems chosen for illustration are in excellent agreement with experimental results. This opens the door for determining DPD interactions using interfacial tension as a fitting parameter.     

Nature of non-radiative processes involved in the excited state of 9-cyanoanthracene in presence of 2-methylindole/2-methylindoline quenchers. A laser flash photolysis study to reveal the medium effects

By using steady state and time-resolved (laser flash photolysis and single photon counting) spectroscopic techniques the quenching of the lowest excited singlet (S1) state of 9-cyanoanthracene (9CNA) by the donors (quenchers) 2-methylindole (2MI) and 2-methylindoline (2MIN) in solvents of different polarity has been studied. Both the transient absorption, by laser flash photolysis technique, and photobleaching measurements were made at the ambient temperature both in non-polar n-heptane (NH) and highly polar acetonitrile (ACN) solvents. The photobleaching efficiency (alpha) was found to depend significantly on the polarity of surrounding solvents and also on the molecular structures of the quenchers. In NH the values of alpha are found to be larger than the corresponding values observed in ACN for both 2MI and 2MIN which possess highly reactive H atom bound to the heterocyclic N atom. Following the results obtained from the transient absorption spectra of the present donor-acceptor molecules in the different polarity solvents, a scheme describing the overall reaction mechanisms of the different photoreactions involved has been proposed. The probable causes for the changes observed in the mechanisms of the photoreactions involved in the cases of 2MI and 2MIN donors have been discussed in the light of their canonical structures.     

Donor–acceptor complexes in copolymerization. XLIX. Cationic polymerization of donor monomers in presence of polar solvents and acrylic monomers. A revised mechanism for polymerization of comonomer complexes

α-Methylstyrene (MS) and isobutyl vinyl ether (VE) readily polymerize, styrene (S) polymerizes to a small extent, and isobutylene (IB), butadiene (BD), and isoprene (IP) fail to polymerize in the presence of catalytic amounts of AlCl₃ when propionitrile, ethyl propionate, and methyl isobutyrate are used as reaction media. MS polymerizes readily and S polymerizes with difficulty in the presence of AlCl₃ to yield homopolymers when acrylonitrile (AN) is present and copolymers with ethyl acrylate (EA) and methyl methacrylate (MMA). VE readily homopolymerizes, while IB, BD, and IP fail to polymerize in the presence of AlCl₃ and the acrylic monomers. VE readily homopolymerizes, S and MS polymerize to a very small extent, and IB, BD, and IP do not polymerize in the presence of ethylaluminum sesquichloride (EASC) in polar solvents. VE readily homopolymerizes in the presence of EASC and the acrylic monomers. MS polymerizes to a small extent in the presence of EASC and the acrylic monomers to yield equimolar copolymers with EA and MMA and a mixture of cationic homopolymer and equimolar copolymer with AN. S yields equimolar copolymers in low yield in the presence of EASC and the acrylic monomers. IB, BD, and IP in the presence of EASC do not polymerize to any significant extent when EA is present, form AN-rich copolymers and yield poly(methyl methacrylate) in the presence of MMA. A revised mechanism is presented for the formation of cationic, radical, random, and alternating copolymers as well as alternating copolymer graft copolymers in the copolymerization of donor and acceptor monomers.     

Activation of gold on titania: adsorption and reaction of SO(2) on Au/TiO(2)(110)

Synchrotron-based high-resolution photoemission and first-principles density-functional slab calculations were used to study the interaction of gold with titania and the chemistry of SO(2) on Au/TiO(2)(110) surfaces. The deposition of Au nanoparticles on TiO(2)(110) produces a system with an extraordinary ability to adsorb and dissociate SO(2). In this respect, Au/TiO(2) is much more chemically active than metallic gold or stoichiometric titania. On Au(111) and rough polycrystalline surfaces of gold, SO(2) bonds weakly and desorbs intact at temperatures below 200 K. For the adsorption of SO(2) on TiO(2)(110) at 300 K, SO(4) is the only product (SO(2) + O(oxide) --> SO(4,ads)). In contrast, Au/TiO(2)(110) surfaces (theta;(Au) < or = 0.5 ML) fully dissociate the SO(2) molecule under identical reaction conditions. Interactions with titania electronically perturb gold, making it more chemically active. Furthermore, our experimental and theoretical results show quite clearly that not only gold is perturbed when gold and titania interact. The adsorbed gold, on its part, enhances the reactivity of titania by facilitating the migration of O vacancies from the bulk to the surface of the oxide. In general, the complex coupling of these phenomena must be taken into consideration when trying to explain the unusual chemical and catalytic activity of Au/TiO(2). In many situations, the oxide support can be much more than a simple spectator.     

Facile catalyzed acylation of alcohols, phenols, amines and thiols based on ZrOCl2·8H2O and acetyl chloride in solution and in solvent-free conditions

Acylation of heteroatoms (O, N and S) with acetyl chloride based on the use of a catalytic amount of the moisture stable, inexpensive ZrOCl₂·8H₂O, proceeds efficiently producing the corresponding acylated products in excellent yields.     

Fluorination of polymers by sulfur hexafluoride gas under electric discharge

Fluorination of low-density polyethylene, polyacetylene, and poly(vinyl alcohol) was carried out using SF₆ gas under electric discharge. The polymers were partially fluorinated and the extent of fluorination was more in the case of poly (vinyl alcohol) than the other two polymers. The fluorinated polymers were characterized by elemental analysis (Fluorine), IR, and x-ray diffraction. Optical transparency of the films was also measured. The fluorinated polymers show better solvent resistance and decreased transparency than the virgin polymer. © 1994 John Wiley & Sons, Inc.     

Processable heat-resistant polymers. XI. Synthesis and characterization of unsaturated polyamideimides

Polycondensation of the diacid chloride of 2-(3-carboxy vinyl)phenyl-1,3-dioxoisoindoline-5-carboxylic acid with m-phenylenediamine and the diacid chloride of 2-(4-carboxy phenyl)-1,3-dioxoisoindoline-5-carboxylic acid with 1,5-bis(3-aminophenyl)1,4-pentadien-3-one was carried out in polar solvents to produce new unsaturated polyamide–imides. The solution and the thermal, electrical, and a few other properties of the polymers were studies. The polymers were soluble in highly polar solvents. The solubility parameter of the polymers was calculated from the Small's group contribution. The polymers were fairly thermostable and underwent crosslinking creaction when heated, preferably in the presence of a suitable catalyst. The crosslinked polymers were in soluble even in highly polar solvents and possessed higher thermal stability. The swelling behavior of the polymers was studied and the molecular weight between two consecutive crosslinks was determined. X-ray diffraction and the dielectric properties of the polymers and their crosslinked products were also studied.     

Constrained photophysics of 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine in micellar environments: a spectrofluorometric study

Photophysical properties of 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ) have been studied in different aqueous micellar environments using steady-state and time-resolved emission spectroscopy. The charge transfer (CT) fluorescence exhibits appreciable hypsochromic shift, along with an enhancement in the fluorescence intensity in all the micellar media. This is associated with an increase in the fluorescence anisotropy (r), which suggests that the fluorophore molecule experiences motionally restricted environments upon binding with the micelles. Fluorescence spectral position and fluorescence quenching studies suggest that the fluorescing moiety does not penetrate into the core of the micellar units; rather it binds at the micelle-water interfacial region. The binding constant and free energy change during probe-micelle binding have been evaluated from relevant fluorescence data. Light has been thrown on the mode of action of urea on micelle bound probes. The results are interpreted in terms of the model that urea displaces water molecules from the micellar interface and the consequent destabilization leads to the expulsion of the probe molecules from the interfacial region. Polarity and viscosity of the microenvironments around the probe have been determined in the micellar systems.     

Accessing C2-Functionalized 1,3-(Benz)azoles through Transition Metal-Catalyzed C−H Activation

The skeletal presence of 1,3-azoles in a variety of bioactive natural products, pharmacophores, and organic materials demands the derivatization of such heteroarenes regioselectively. Plenty of cross-coupling as well as cyclocondensation reactions have been performed to build up these skeletons but remained commercially unrealizable. A couple of severe drawbacks are faced by these traditional protocols that require a more straightforward strategy to obviate them. Transition metal-catalyzed C−H functionalization has emerged as a superior alternative in that context. 1,3-Azoles and their benzo counterparts have been extensively functionalized exploiting both noble and earth-abundant transition metals. Lately, C-2 functionalization have gained much traction due to the ease of attaining high regioselectivity and installation of synthetically manipulative functionalities. This critical review presents a bird‘s eye view of all major C-2 functionalization of (benz)azoles catalyzed by a diverse set of metals performed over the past 15 years.