H NMR Dynamic study of thermal Z/E isomerization of 5-substituted 2-alkylidene-4-oxothiazolidine derivatives: Barriers to rotation about CC bond

The rotational barriers between the configurational isomers of two structurally related push–pull 4-oxothiazolidines, differing in the number of exocyclic CC bonds, have been determined by dynamic ¹H NMR spectroscopy. The equilibrium mixture of (5-ethoxycarbonylmethyl-4-oxothiazolidin-2-ylidene)-1-phenylethanone (1a) in CDCl₃ at room temperature to 333 K consists of the E- and Z-isomers which are separated by an energy barrier ΔG^# 98.5 kJ/mol (at 298 K). The variable-temperature ¹H NMR data for the isomerization of ethyl (5-ethoxycarbonylmethylidene-4-oxothiazolidin-2-ylidene)ethanoate (2b) in DMSO-d₆, possessing the two exocyclic CC bonds at the C(2)- and C(5)-positions, indicate that the rotational barrier ΔG^# separating the (2E,5Z)-2b and (2Z,5Z)-2b isomers is 100.2 kJ/mol (at 298 K). In a polar solvent-dependent equilibrium the major (2Z,5Z)-form (>90%) is stabilized by the intermolecular resonance-assisted hydrogen bonding and strong 1,5-type S · · · O interactions within the SCCCO entity. The ¹³C NMR Δδ_C(2)C(2′) values, ranging from 58 to 69 ppm in 1a–d and 49-58 ppm in 2a–d, correlate with the degree of the push-pull character of the exocyclic C(2)C(2′) bond, which increases with the electron withdrawing ability of the substituents at the vinylic C(2′) position in the following order: COPh COEt > CONHPh > CONHCH₂CH₂Ph. The decrease of the Δδ_C(2)C(2′) values in 2a–d has been discussed for the first time in terms of an estimation of the electron donor capacity of the S fragment on the polarization of the CC bonds.     

A bonding study of cyclopentene (c-C5H8) adsorption on Ni(1 1 1) surface

The adsorption of cyclopentene (c-C₅H₈) on Ni(1 1 1) was studied using DFT and semiempirical calculations. Preferred site and geometry calculations were carried out considering a Ni(1 1 1) surface and a unit cell of 64-atoms. The tetrahedral threefold hollow position was identified as the most favorable site, with a surface-molecule minimum distance of 1.83 Å. A bending structure is adopted when the molecule is adsorbed where the carbon atoms of the double bond are closer to the surface forming an angle of 160° among non-equivalents carbon atoms. The metal surface was represented by a two-dimensional slab with an overlayer of c-C₅H₈/Ni of 1/9 ratio. We also computed the density of states (DOS) and the crystal orbital overlap populations (COOP) corresponding to CC, CNi, CH, and NiNi bonds. We found that both NiNi bonds interacting with the ring, and the CC bond are weakened after adsorption, this last bond is linked significantly to the surface. The hydrogen atoms belonging to the saturated carbon atoms also participate in the adsorbate–surface bonding. The main interactions include the 4s, 3p_z and 5d_z² bands of nickel and 2p_z bands of the carbon atoms of the double bond.     

Improved thermal stability of crosslinked PTFE using fluorine gas treatment

Crosslinked PTFE (XF) samples were fluorinated at 293-593 K under 0.7-101 kPa F₂ and for 1 h to 7 days to improve its thermal stability. Because the weight uptake which may be caused by the fluorine addition was detected at room temperature, CC bonds in XF can be fluorinated and the fluorine content was saturated after 72 h. Weights of all samples increased more than that of original XF through additional fluorination of CC bonds, whereas it decreased by the chain-scission to form gaseous fluorocarbons such as CF₄. The intensity ratio in IR spectra of the peaks correspond to the double bond (CFCF₂) at 1785 cm⁻¹ and the characteristic peaks of PTFE at 1794 cm⁻¹, I_PTFE/I_PTFE was smaller for the fluorinated XF rather than that for XF. Average values of heat of crystallization (ΔH_c) for all fluorinated XF samples were about 2 J/g higher than that of the original XF. The decomposition temperature calculated from the TG curves increased with increasing reaction temperature and reaction time up to 72 h. Thermal stability of XF was improved through fluorine gas treatment.     

A computational study of the effect of an external electric field on the geometry of selected donor–acceptor complexes

To understand the effect of Au and thiol atoms in octane molecule, a structural and charge density analysis has been carried out by high level ab initio quantum chemical calculations using MP2 and B3PW91 methods with the basis sets 6-311G(d,p) and LANL2DZ. The optimized geometries, specifically, the geometry obtained from both levels reveal the effect of S- and Au-atoms in octane molecule. An introduction of sulfur atom in octane molecule lengthen its backbone C–C bond distances, and further adding of Au-atom at the terminals of octane dithiolate stabilizes these distances. The bond densities of the C–C bonds of octane are 1.6 eÅ⁻³, these values are decreased significantly and the charges are largely depleted, when thiol and Au-atoms added in the octane molecule. The presence of negative Laplacian ²ρ(r) at bond critical points of C–C and C–H bonds, indicate, the charges are concentrated in these bonds, confirm that these bonds exhibit an open shell type interaction. The moderate values of density and the negative Laplacian of S–C bonds confirm the covalent character. The positive ²ρ(r) value of Au–S bonds, characterize, the bonding interaction is a closed shell interaction. The combined observed low value of electron density and the positive Laplacian of Au–S bond comprises, the gold and S interaction is not a covalent interaction, but it is a very weak coordination bond interaction. The small positive value of total energy density in Au–S bond indicates, the charges in these bonds are highly depleted and this is further confirmed by the Laplacian of bond characterization.     

Synthesis and Structure of Cyclopropenone π-Complexes with Pentacarbonyliron(0) and Hexacarbonyltungsten(0). Hydrophosphorylation of Cyclopropenone in the Transition Metal Coordination Sphere

New -complexes of pentacarbonyliron(0) and hexacarbonyltungsten(0) containing ²-coordinated cyclopropenone molecules were synthesized. The geometric, electronic structure, and energy parameters of the coordinated cyclic oxo diene were determined by nonempirical quantum-chemical methods. According to the theoretical and experimental (IR and NMR) data, the conjugation between the double carbon-carbon and carbon-oxygen bonds is broken as a result of coordination. The coordinated cyclopropenone reacts with dialkyl hydrogen phosphites to give the corresponding -hydroxyphosphonate via addition at the carbonyl group, whereas hydrophosphorylation of the free ligand occurs at the double carbon-carbon bond.     

The investigation of argon plasma surface modification to polyethylene: Quantitative ATR-FTIR spectroscopic analysis

This paper studied the surface modification of argon plasma to polyethylene by using ATR-FTIR analysis. The mass loss ratio has maximum value at discharge time of 70-120 s or discharge power of 62 W by using argon plasma treatment for polyethylene. New surface structure was formed after polyethylene was treated by argon plasma. The peroxide bond peak area also has maximum value at discharge time of 70-120 s or discharge power of 62 W. The CC nonsaturated double bond absorb peaks were appeared at 1640 cm⁻¹, 1549 cm⁻¹ and 1528 cm⁻¹ after polyethylene treated by argon plasma. The CC nonsaturated double bond absorb peak area has minimum value at discharge time of 60-70 s and the power of 65 W. The CC nonsaturated double bond absorb peak area has maximum value at discharge power of 62-72 W and the discharge time of 2 min. The absorption peak intensity of 2916 cm⁻¹ methylene nonsymmetry stretch vibration, 2848 cm⁻¹ methylene symmetry stretch vibration, 1463 cm⁻¹ methylene nonsymmetry changing angle vibration, and 719 cm⁻¹ methylene swing in plane vibration was decreased greatly. The four absorption peaks intensity has maximum value at discharge time of 120 s or discharge power of 62 W.     

Hyperpolarizability of donor-acceptor azines subject to push-pull character and steric hindrance

The push-pull character of two series of donor-acceptor azines has been quantified by ¹³C, ¹⁵N chemical shift differences of the partial C(1)N(1) and N(2)C(2) double bonds in the central linking C(1)N(1)-N(2)C(2) unit and by the quotient of the occupations of the bonding π and anti-bonding π^∗ orbitals of these bonds. Excellent correlation of the latter push-pull parameter with the corresponding bond lengths d_CN strongly recommend both the occupation quotients π^∗/π and the corresponding bond lengths as reasonable sensors for quantifying the push, pull character along the CN-NC linking unit, for the donor-acceptor quality of the two series of azines and for the molecular hyperpolarizability ß₀ of these compounds. Within this context, reasonable conclusions concerning the interplay of steric hindrance in the chromophore, push-pull character and hyperpolarizability of the azines and their application as NLO materials will be drawn.     

NMR spectroscopic study of rotation around CC and C?N bonds in diene δ-aminocarbonyl compounds

A relatively fast rotation around the α,β carbon–carbon double bond at the equilibrium of geometrical isomers and a comparatively slow rotation around the carbon-nitrogen single bond in compounds of the type (X₁, X₂ are electron-attracting substituents) were detected and investigated by the NMR technique. The relationships between the free energies of activation for these rotational processes and the character of the substituents, the number of double bonds, solvents and concentration were studied.     

Synthesis, characterization and photovoltaic properties of thiophene copolymers containing conjugated side-chain

Five side-chain conjugated polythiophene derivatives, P1-P5, were synthesized by Stille coupling reaction. The effects of side-chain structures, bearing CC double bond, CC triple bond as well as different number of methoxy substituents on the benzene ring of the side-chains, on the optical, electrochemical, and photovoltaic properties of the polymers were investigated. From P1 to P3, the effect of CC triple bond and CC double bond was compared. The results indicate that the content of the thiophene units with the CC triple bond in their conjugated side-chains not only influences the absorption shape and intensity, but also influences the energy bandgap and the photovoltaic properties of the polymers. From P3 to P5, the effect of methoxy substituents on the benzene ring of the conjugated side-chains was compared. On increasing the number of the methoxy groups on the benzene ring of the conjugated side chains, the visible π-π^∗ absorption of the conjugated polymer backbone become stronger both in solution and in film. Electron-donating ability of the methoxy groups decreased the bandgap of the polymers. The best polymer solar cell based on P5 with a structure of ITO/PEDOT:PSS/Polymer:PCBM (1:1 wt/wt)/Mg/Al showed a power conversion efficiency of 1.45% under the illumination of AM1.5, 80 mW/cm².     

Adsorption of Cationic Polyelectrolyte on Quartz from Aqueous Background Electrolyte Solution at pH 3

Adsorption isotherm of cationic polyelectrolyte, poly(styrene-co-dimethylaminopropylmaleimide), (molecular mass is 2 × 10⁴) on the surface of fused quartz in aqueous 10^–4 M KCl solution at pH 3 was measured by the method of capillary electrokinetics. The limiting coverage of adsorption layer corresponds to surface charge ₀ = 0.82 C/mol that exceeds the value obtained earlier at pH 6.5. However, if one takes into account the higher charge of a macromolecule at pH 3, the values of packing density of copolymer molecules in completely filled adlayers appeared to be close: 7.88 × 10¹⁰ at pH 3 and 7.27 × 10¹⁰ cm^–2 at pH 6.5. The average binding energy of the molecules and the quartz surface calculated by the Langmuir equation is equal approximately to 21kT and lies between the values of the energy of electrostatic (25.4kT) and hydrophobic (17.7kT) adsorption at pH 6.5 calculated earlier. It can be assumed that, at pH 3, charged units of a macromolecule form ion–dipole bonds with silanol groups, while uncharged groups form hydrophobic bonds with siloxane surface sites.     

Vibrational spectroscopy of 4-hydroxybenzhydrazide and its O,N-deuterated isotopologue accompanied by X-ray structure refinement

The vibrations of crystalline 4-hydroxybenzhydrazide were investigated by IR and Raman spectroscopy. Spectral changes resulting from O,N-deuteration together with DFT calculations were employed for band assignment presented in terms of potential energy distribution. The characteristic absorptions of the hydrazide group were located at 1623 (CO stretching), 1588 (NH₂ bending) and 1532 cm⁻¹ (NH bending). The greatest contributions of the NN and CN stretching vibrations were found in the 1208 and 1109 cm⁻¹ modes, respectively. The predominant contribution of the CO stretching vibration was observed for the 1282 cm⁻¹ absorption. The computations at the B3LYP level with 6-311++G(d,p) basis set were based on structural parameters taken from refined single crystal X-ray investigations. The details of hydrogen bonding and crystal packing are also presented.     

The surface structure of sulfated zirconia: Studies of XPS and thermal analysis

Sulfated zirconias were prepared using two kinds of amorphous zirconia gels, XZO 631 and 632 supplied by MEL Chemicals, and their thermal gravimetrical analyses were carried out. DTG of the former sample showed two peaks based on decomposition of the sulfate species on the surface, the first peak at 680 °C and the second broad one centered at 850 °C. The latter sample indicated only broad peak at 850 °C in the range from 700 to >1000 °C. The first peak for the former sample was ascribed to the decomposition of Zr(SO₄)₂ remained on the surface, and the broad one at 700 to >1000 °C for the both samples was attributed to the catalytically active species. The acidic character of sulfated zirconia calcined at 1000 °C was examined in acid-catalyzed reactions of cumene, ethylbenzene, and butane together with the adsorption heat of Ar, showing a solid acid with acidity higher than that of silica-alumina. It was indicated from the XPS analysis that the S species are composed of SO₄²⁻. The results led to a structural model of the active surface to be polysulfate species containing mainly three or four S atoms with two ionic bonds of SOZr in addition to coordination bonds of SO with Zr, the active site being Lewis sites on the S atoms.     

Variable temperature H NMR studies on Grubbs catalysts

Variable temperature ¹H NMR studies were conducted to investigate whether steric congestion is influencing the structural rigidity of (IMesH₂)(PCy₃)(Cl)₂RuCHPh (IMesH₂ = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) in solution. It was shown that both mesityl ligands rotate at about the same rate around the N-Mesityl bonds in the IMesH₂ ligand and that changing the solvent does not significantly alter this rotation. It was found that the increased steric congestion in (IMesH₂)(PCy₃)(Cl)₂RuCHPh compared to (PCy₃)₂(Cl)₂RuCHPh does affect the rates of rotation around the C_alkylidene-Ph bonds. Unusual chemical shift positions were also observed in the low temperature ¹H NMR spectrum for the aromatic proton signals for (IMesH₂)(PCy₃)(Cl)₂RuCHPh and (PCy₃)₂(Cl)₂RuCHPh.     

Electrochemical Studies of the Benzoate Adsorption on Au (111) Electrode

Cyclic voltammetry (CV), differential capacity (DC), and charge densitymeasurements have been employed to study the benzoate (BZ) adsorption at the Au(111)electrode surface. Thermodynamic analysis of charge density (_M) data has beenperformed to describe the properties of the adsorbed benzoate ion. The Gibbsexcess , Gibbs energy of adsorption G, and the number of electrons flowingto the interface per adsorbed benzoate ion at a constant potential (electrosorptionvalency) and at a constant bulk concentration of the benzoate (reciprocal of theEsin—Markov coefficient) have been determined. The results demonstrate thatalthough benzoate adsorption starts at negative charge densities, it takes placepredominantly at a positively charged surface. At the most positive potentials,the surface concentration of benzoate attains a limiting value of about 7.3×10^–10mol-cm^–2, which is independent of the bulk benzoate concentration. This valueis consistent with packing density corresponding to a closed-packed monolayerof vertically adsorbed benzoate molecules. At negative charge densities, benzoateassumes a flat (-bonded) surface coordination. The surface coordination ofbenzoate changes, by moving from a negatively to positively charged surface.At the negatively charged surface, the electrosorption bond is quite polar. Thepolarity of the chemisorption bond is significantly reduced due either to a chargetransfer or a screening of the charge on the anion by the charge on the metal.     

The formation of three-center bonds in chemisorption

Summary It is proposed that molecular adsorption may be brought about by the formation of three-center bonds. In this two donor-acceptor bonds are formed between the molecule to be adsorbed and an atom in the adsorbent surface. The molecule to be adsorbed, for instance, ethylene, acts as a donor because of its -electron pair and the adsorbent atom because of its p-orbital. At the same time the adsorbent atom is a donor on account of its electron pair in a d_XZ-orbital and the molecule an acceptor on account of its antibonding ¹-²- orbital; by this a dative bond is formed. In the case of a metal without d-electrons (for instance, Al) a dative bond is impossible, but the metal can give an acceptor bond because of its empty p-orbital.Such a three-center chemisorption must proceed with a small activation energy, that is, be reversible, unactivated and rapid. Most often chemisorption at low temperature has these properties. The heat of such a chemisorption may vary between a few times ten or a few kcal.Three-center chemisorption may be of considerable importance in catalytic reactions and also in exchange processes on the surface.Only a considerable activation energy and a very high heat of adsorption is a reliable proof that the adsorbed substance occurs on the surface as atoms or in a state in which one adsorbent atom forms a stable chemical bond with only one adsorbate atom.Translated from Zhurnal Strukturnoi Khimii, Vol. 1. No. 2, pp. 189–199, July–August, 1960     

Rh(II)-Cp-TsDPEN catalyzed aqueous asymmetric transfer hydrogenation of chromenones into saturated alcohol: CC and CO reduction in one step

As an efficient catalyst for asymmetric transfer hydrogenation reaction (ATH reaction) of α,β-unsaturated ketones, Rh-Cp^∗-TsDPEN (Cp^∗ = 1,2,3,4,5-pentamethylcyclopenta-1,3-diene, TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenyl- ethylenediamine) shows high chemoselectivity on CO and CC reduction. In our method, both CO and CC bonds in a variety of chromenone derivatives were reduced efficiently in aqueous media, resulting in at least 98% ee and up to 99% yields in a convenient way without further purification. The product was a useful intermediate for deriving chiral chroman-4-amine, which was reported as an effective agent against hypotension and inflammatory pain by inhibiting human bradykinin B1 receptor.     

Unprecedented rearrangement during the formation of P-P homoatomic N-phosphino formamidine complexes

A variety of homoatomic P-P donor-acceptor homoleptic (R = R′) and heteroleptic (R ≠ R′) N-phosphino formamidine complexes [iPr₂N-C(H)N-PR₂-PR′₂]Cl were synthesized from the addition of N-phosphino formamidine (phosfam) donor reagent iPr₂N-C(H)N-PR₂ on halogenophosphane compounds R′₂PCl which are synthetic sources for the corresponding phosphenium derivatives R₂P⁺. We have demonstrated that the dynamic equilibrium observed between the different species is shifted either completely to the side of the free species or to the side of the donor-acceptor adduct [iPr₂N-C(H)N-PPh₂-PPh₂]Cl by changing the solvent or by varying the temperature. Activation parameters of ΔS^≠ = (−130 ± 7.2) J mol⁻¹ K⁻¹, ΔH^≠ = (8.4 ± 0.6) kJ mol⁻¹ and ΔG^≠ (298.15 K) = (53.6 ± 2.3) kJ mol⁻¹ were determined by an Eyring analysis over the temperature range of 193-293 K. The negative entropy of activation is consistent with an associative pathway and the low value of ΔH^≠ suggests that the energy barrier for this reaction is entropically controlled. Phosphine-phosphenium adducts is the most appropriate term to describe the dynamic process observed at variable temperature for complexes [iPr₂N-C(H)N-PR₂ → PR′₂]⁺, but the ³¹P NMR chemical shift and the calculated electronic charges are more in favor of a phosphinophosphonium Lewis drawing [iPr₂N-C(H)N-PR₂-PR′₂]⁺. Formation of the homoatomic P-P heteroleptic formamidine complexes [iPr₂N-C(H)NPR′₂PR₂]Cl (R = Ph, R′ = Et, iPr) results in the formal insertion of the phosphino group of the corresponding alkyl chlorophosphanes R′₂PCl into the N-P bond of the starting phosfam ligand iPr₂N-C(H)N-PR₂. Computed data are in agreement with the transient formation of a heteroatomic N-P intermediate [iPr₂N-C(H)N(PR₂)PR′₂]Cl, which then rearranges to the more thermodynamically favored homoatomic P-P compound [iPr₂N-C(H)N-PR₂-PR′₂]Cl.     

One-step CN, CO bonds cleavage and CO, CN bonds formation over supported ionic liquid in water

At ambient reaction temperature, the silica gel confined ionic liquid catalysts were perfectly combined with water as an effective catalytic system for simultaneous CN and CO bonds transformation with a TONs exceeding 300 mol mol⁻¹.     

Energy of the C = C Double Bond

Determination of the bond energy as the difference between the experimental energy of the double bond and standard value of the C-C bond energy does not take into account changes in the energy of the C-C bond as it becomes shorter. The change in the single bond energy upon its shortening by 0.2 Å was evaluated from the compressibilities of diamond and polyethylene, and also by quantum-chemical calculations. With this value taken into account, the energies of the and bonds in ethylene become close, which proves the equivalence of the traditional and banana models of the C = C bond.     

Synthesis of macrocyclic polyethers via Ru complex-catalyzed metathesis cyclization and their use as the ring component of rotaxanes

Ring closing metathesis of the vinyl group-terminated oligoethers catalyzed by RuCl₂(CHPh)(PCy₃)₂ yielded macrocyclic polyethers containing vinylene group. The ¹H and ¹³C NMR spectra indicated the presence of CC double bond (trans/cis = ca. 80:20). The obtained 23-membered cyclic ether reacted with benzyl(anthrylmethl)ammonium hexafluorophosphate to produce the pseudo-rotaxane as colorless crystals. X-ray crystallography revealed N–H⋯O hydrogen bonds and stacking of the aromatic planes between the host and guest molecules, which stabilized the rotaxane structure in the solid state.