13C Nuclear Magnetic Resonance Studies of the Conformations of Serine‐3′‐ and 5′‐Thymidine Monophosphate Conjugates

The differences in the backbone conformation between O‐thymidine‐3′‐(1) and 5′‐yl O‐alkyl N‐phosphoryl serine methyl esters (2) have been investigated by solution ¹³C NMR spectroscopy. The stereo‐sensitive vicinal ³¹P–¹³C coupling constants were measured and used in the conformational analysis for the P–O5′–C5′, P–O3′–C3′, and P–N–C_α bonds. Three‐dimensional structural characteristics of dephosphorylation reactions of Compounds are also discussed.     

Steric effects on the mechanism of reaction of nucleophilic substitution of β‐substituted alkoxyvinyl trifluoromethyl ketones with four secondary amines

The kinetics of the reaction of β‐substituted β‐alkoxyvinyl trifluoromethyl ketones R¹O‐CR²?CH‐COCF₃ ( 1a – e ) [( 1a ), R¹?C₂H₅, R²?H; ( 1b ), R¹?R²?CH₃; ( 1c ), R¹?C₂H₅, R²?C₆H₅; ( 1d ), R¹?C₂H₅, R²?V^?pNO₂C₆H₄; ( 1e ), R¹?C₂H₅, R²?C(CH₃)₃] with four aliphatic amines ( 2a – d ) [( 2a ), (C₂H₅)₂NH; ( 2b ), (i‐C₃H₇)₂NH; ( 2c ), (CH₂)₅NH; ( 2d ), O(CH₂CH₂)₂NH] was studied in two aprotic solvents, hexane and acetonitrile. The least reactive stereoisomeric form of ( 1a – d ) was the most populated ( E‐s‐Z‐o‐Z ) form, whereas in ( 1e ), the more reactive form ( Z‐s‐Z‐o‐Z ) dominated. The reactions studied proceeded via common transition state formation whose decomposition occurred by ‘uncatalyzed’ and/or ‘catalyzed’ route. Shielding of the reaction centre by bulky β‐substituents lowered abruptly both k′ (‘uncatalyzed’ rate constant) and k″ (‘catalyzed’ rate constant) of this reaction. Bulky amines reduced k″ to a greater extent than k′ as a result of an additional steric retardation to the approach of the bulky amine to its ammonium ion in the transition state. An increase in the electron‐withdrawing ability of the β‐substituent increased ‘uncatalyzed’ k′ due to the acceleration of the initial nucleophile attack (k₁) and ‘uncatalyzed’ decomposition of transition state (k₂) via promoting electrophilic assistance (through transition state 8 ). The amine basicity determined the route of the reaction: the higher amine basicity, the higher k₃/k₂ ratio (a measure of the ‘catalyzed’ route contribution as compared to the ‘uncatalyzed’ process) was. ‘Uncatalyzed’ route predominated for all reactions; however in polar acetonitrile the contribution of the ‘catalyzed’ route was significant for amines with high pK_a and small bulk. Copyright © 2007 John Wiley & Sons, Ltd.     

The Field-Dependent Magnetization of d5–d7 Metal β−Diketonate Complexes and Their Macromolecular Polymers

A vibrating sample magnetometer (VSM) has been used to study the field-dependent magnetization, M(H), of the d⁵?d⁷ metal acetates [M(OAc)₂.nH₂O], metal β?diketonate complexes [M(tba)₂(H₂O)₂] and the macromolecular polymers [M(tba)₂(4,4-bipy)]_n (where, M = Mn(II), Fe(II), and Co(II), OAc = O₂CCH₃, tba = deprotonated 3-benzoyl-1.1.1-trifluoroacetone, and 4,4-bipy = 4,4′-bipyridine). The magnetic field strength (H) was applied in the range of 0?10⁴ O_e at ambient temperature (ca. 23°C). The experimental results showed that the d⁵?d⁷ metal acetate, complexes and polymers exhibit low paramagnetic properties excepting [Fe(tba)₂(4,4-bipy)]_n polymer, which had negative magnetization M(emu/g) showing diamagnetic properties in the range 0?10⁴ O_e. The magnetization was almost equal to zero without an applied magnetic field (H(O_e)) for each d⁵?d⁷ metal acetate, complex, and polymer. The linear M(H) curve had a magnetic saturation for iron and manganese acetate species at the magnetic field strengths of 3.1 × 10³ and 4.7 × 10³ Oe, respectively. The external magnetic field reached 9.0 × 10³ O_e without any saturation magnetization for the cobalt compounds. The coordination effect of 3-benzoyl-1.1.1-trifluoroacetone (H-tba) and 4,4′-bipyridine (4,4′-bipy) ligands on the field-dependent magnetization M(H) and paramagnetic behavior of d⁵?d⁷ metal atoms is discussed. The field-dependent magnetization M(H) curves of metal β?diketonate complexes and the polymers including d⁵?d⁷ metal acetates showed a weak field octahedral geometry.     

Structural Assignment of Stilbenethiols and Chalconethiols and Differentiation of Their Isomeric Derivatives by Means of 1H‐ and 13C‐NMR Spectroscopy

Abstract

The ¹H‐ and ¹³C‐NMR spectra of some substituted stilbenes and chalcones were assigned unambiguously on the basis of a combination of homo‐ (COSY) and heteronuclear (HETCOR) two‐dimensional methods, the chemical shifts, as well as spin‐coupling constants. The A_ik empirical parameters of the –O–C(S)–N(CH₃)₂, –S–C(O)–N(CH₃)₂, and –SH group were calculated to help predict the chemical shifts of substituted stilbenes, 4′‐nitrostilbenes, and chalcones. The ¹H‐ and ¹³C‐NMR spectra have been shown to be able to differentiate between the isomers of O‐stilbenyl (4, 5) and S‐stilbenyl N,N‐dimethylthiocarbamates (7, 8) as well as O‐chalconyl (6) and S‐chalconyl N,N‐dimethylthiocarbamates (9).     

Influence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: a time‐resolved resonance Raman and density functional theory study

A nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopic investigation of the photoreduction reactions and ability of several chloro‐substituted benzophenone (Cl‐BP) triplets is described. The TR³ results show that the 3‐chlorobenzophenone (3‐Cl‐BP), 4‐chlorobenzophenone (4‐Cl‐BP) and 4,4′‐dichlorobenzophenone (4,4′‐dichloro‐BP) triplets exhibit similar hydrogen abstraction ability with the parent BP triplet. In 2‐propanol, the 3‐Cl‐, 4‐Cl‐ and 4,4′‐dichloro‐diphenylketyl (DPK) radicals were observed and they appear to react with dimethylketyl radicals at the para‐position to form a light absorption transient species. These transient species were characterized with TR³ spectra, and identified with the help of results from density functional theory calculations. In an acetontitrile/water (MeCN:H₂O) 1:1 mixed solvent, these DPK radicals were also observed but with slower formation rates. However, the 2‐Cl‐DPK radical was observed to form with a lower yield and a significantly slower formation rate than the other chloro‐substituted benzophenones examined here in 2‐propanol under the same experimental conditions. These results reveal that the 2‐chloro substituent reduces the hydrogen abstraction ability of the substituted BP triplet, which was not as expected based on the assumption that the electron‐withdrawing group could increase its photoreduction ability. This unusual ortho effect of the chlorine substitution is briefly discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

A DFT study on Diels–Alder cycloadditions of trans‐1,3‐butadiene to C60 and C70

Investigation of the relative reactivity of bonds in fullerenes will provide fundamental theory for the design of fullerene‐based materials. We have theoretically investigated the reactivity of the Diels–Alder (DA) cycloaddition of cis‐1,3‐butadiene to all types of bonds in C₆₀ and C₇₀ using the M06‐2X hybrid density functional theory (DFT) calculations (J. Phys. Org. Chem. 2012, 25 850–855) and have pointed out that the DA cycloadditions of cis and trans forms of 1,3‐butadiene to ethylene have a specially intimate relationship (J. Phys. Org. Chem. 2014, 27 652–660). For the aim of telling a whole story of the DA cycloaddition concerning C₆₀ and C₇₀, the DA cycloadditions of trans‐1,3‐butadiene to all types of bonds in C₆₀ and C₇₀ were explored at the same theoretical level as those of the cis‐1,3‐butadiene. The calculated results related with the trans‐ and cis‐1,3‐butadienes were compared. The potential energy curves of DA cycloadditions of trans‐ and cis‐1,3‐butadiene to C₆₀ and C₇₀ were discussed. The distortion–interaction energy model was employed to elucidate the origin of different reactivity of all kinds of C?C bonds. The solvent effects were examined using the continuum solvent model. These current results, along with our previous research, will help to obtain an overall view of the DA cycloadditions of 1,3‐butadiene to C₆₀ and C₇₀. Copyright © 2014 John Wiley & Sons, Ltd.     

Observation of stimulated Raman scattering in polar tetragonal crystals of barium antimony tartrate trihydrate,Ba[Sb2((+)C4H2O6)2]·3H2O

The non‐centrosymmetric polar tetragonal (P 4₁) barium antimony tartrate trihydrate, Ba[Sb₂((+)C₄H₂O₆)₂]·3H₂O, was found to be an attractive novel semi‐organic crystal manifesting numerous χ ⁽²⁾‐ and χ ⁽³⁾‐nonlinear optical interactions. In particular, with picosecond single‐ and dual‐wavelength pumping SHG and THG via cascaded parametric four‐wave processes were observed. High‐order Stokes and anti‐Stokes lasing related to two SRS‐promoting vibration modes of the crystal, with ω_SRS1 ≈ 575 cm^?1 and ω_SRS2 ≈ 2940 cm^?1, takes place. Basing on a spontaneous Raman investigation an assignment of the two SRS‐active vibration modes is discussed.

     

Hartree–Fock and density functional theory study of remote substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of para‐substituted phenoxydicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄O(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄OFp ( 1 ), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted benzenethiolatodicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄S(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄SFp ( 2 )] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free‐energy relations [r = 0.99 (g, 1a), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and Δpk_a's of O–H bonds of p‐G‐C₆H₄OH or ΔΔH_het(Fe‐S)'s and Δpk_a's of S–H bonds of p‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1g), ?0.98 (g, 2h)] among the ΔΔH_het (Fe‐O)'s or ΔΔH_het(Fe‐S)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free‐energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. ΔΔH_het(Fe–O)'s(g) ( 1 ) and ΔΔH_het(Fe–S)'s(g)( 2 ) follow the Capto‐dative principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterization of V3O7⋅H2O nanobelts

V ₃O₇?H₂O nanobelts were prepared by a hydrothermal method at 190 ^°C using V ₂O₅?nH₂O gel and H₂C₂O₄?2H₂O as starting agents. The nanobelts obtained have diameters ranging from 40 to 70 nm with lengths of up to several micrometers. Their morphology and structure have been characterized by XRD, SEM, TEM and IR spectroscopy. The effect of the annealing temperature on the morphology of the resulting product has been investigated. XRD and SEM showed that thermal annealing of the V ₃O₇?H₂O sample in air led to the collapse of the V ₃O₇?H₂O nanobelt structure and the convert into V ₂O₅ nanobelts. For the first time V ₂O₅ nanobelts with an ultrahigh aspect-ratio have been obtained in air. Furthermore, electrical conductivity and static magnetic susceptibility measurements have been carried out.     

Flame structure of laminar premixed anisole flames investigated by photoionization mass spectrometry and photoelectron spectroscopy

Two laminar, premixed, fuel-rich flames fueled by anisole-oxygen-argon mixtures with the same cold gas velocity and pressure were investigated by molecular-beam mass spectrometry at two synchrotron sources where tunable vacuum-ultraviolet radiation enables isomer-resolved photoionization. Decomposition of the very weak O–CH₃ bond in anisole (C₆H₅OCH₃) by unimolecular decomposition yields the resonantly-stabilized phenoxy radical (C₆H₅O). This key intermediate species opens reaction routes to five-membered ring species, such as cyclopentadiene (C₅H₆) and cyclopentadienyl radicals (C₅H₅). Anisole is often discussed as model compound for lignin to study the phenolic-carbon structure in this natural polymer. Measured temperature profiles and mole fractions of many combustion intermediates give detailed information on the flame structure. A very comprehensive reaction mechanism from the literature which includes a sub-scheme for anisole combustion is used for species modeling. Species with the highest measured mole fractions (on the order of 10^?3–10^?2) are CH₃, CH₄, C₂H₂, C₂H₄, C₂H₆, CH₂O, C₅H₅ (cyclopentadienyl radical), C₅H₆ (cyclopentadiene), C₆H₆ (benzene), C₆H₅OH (phenol), and C₆H₅CHO (benzaldehyde). Some are formed in the first destruction steps of anisole, e.g., phenol and benzaldehyde, and their formation will be discussed and with regard to the modeling results. There are three major routes for the fuel destruction: (1) formation of benzaldehyde (C₆H₅CHO), (2) formation of phenol (C₆H₅OH), and (3) unimolecular decomposition of anisole to phenoxy (C₆H₅O) and CH₃ radicals. In the experiment, the phenoxy radical could be measured directly. The phenoxy radical decomposes via a bicyclic structure into the soot precursor C₅H₅ and CO. Formation of larger oxygenated species was observed in both flames. One of them is guaiacol (2-methoxyphenol), which decomposes into fulvenone. The presented speciation data, which contain more than 60 species mole fraction profiles of each flame, give insights into the combustion kinetics of anisole.     

Reactivity of the insecticide chlorpyrifos‐methyl toward hydroxyl and perhydroxyl ion. Effect of cyclodextrins

The reactivity of Chlorpyrifos‐Methyl ( 1 ) toward hydroxyl ion and the α‐nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25 °C in water containing 10% ACN or 7% 1,4‐dioxane at NaOH concentrations between 0.01 and 0.6 M ; the second‐order rate constant is 1.88 × 10^?2 M ^?1 s^?1 in 10% ACN and 1.70 × 10^?2 M ^?1 s^?1 in 7% 1,4‐dioxane. The reaction with H₂O₂ was studied in a pH range from 9.14 to 12.40 in 7% 1,4‐dioxane/H₂O; the second‐order rate constant for the reaction of HOO^? ion is 7.9 M ^?1 s^?1 whereas neutral H₂O₂ does not compete as nucleophile. In all cases quantitative formation of 3,5,6‐trichloro‐2‐pyridinol ( 3 ) was observed indicating an S_N2(P) pathway. The hydrolysis reaction is inhibited by α‐, β‐, and γ‐cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ‐cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α‐ and β‐cyclodextrin (β‐CD), whereas γ‐cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β‐ or γ‐cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin‐mediated reaction is the reaction of HO^? or HOO^? ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

A theoretical assignment on excited‐state intramolecular proton transfer mechanism for quercetin

In the present work, we investigate a new chromophore (ie, quercetin) (Simkovitch et al J Phys Chem B 119 [2015] 10244) about its complex excited‐state intramolecular proton transfer (ESIPT) process based on density functional theory and time‐dependent density functional theory methods. On the basis of the calculation of electron density ρ( r ) and Laplacian ?²ρ( r ) at the bond critical point using atoms‐in‐molecule theory, the intramolecular hydrogen bonds (O₁‐H₂?O₅ and O₃‐H₄?O₅) have been supported to be formed in the S₀ state. Comparing the prime structural variations of quercetin involved in its 2 intramolecular hydrogen bonds, we find that these 2 hydrogen bonds should be strengthened in the S₁ state, which is a fundamental precondition for facilitating the ESIPT process. Concomitantly, infrared vibrational spectra analysis further verifies this viewpoint. In good agreement with previous experimental spectra results, we find that quercetin reveals 2 kinds of excited‐state structures (quercetin* and quercetin‐PT1*) in the S₁ state. Frontier molecular orbitals depict the nature of electronically excited state and support the ESIPT reaction. Our scanned potential energy curves according to variational O₁‐H₂ and O₃‐H₄ coordinates demonstrate that the proton transfer process should be more likely to occur in the S₁ state via hydrogen bond wire O₁‐H₂?O₅ rather than O₃‐H₄?O₅ because of the lower potential energy barrier 2.3 kcal/mol. Our present work explains previous experimental result and makes up the deficiency of mechanism in previous experiment. In the end, we make a reasonable assignment for ESIPT process of quercetin.     

Reactivity of mixed organozinc and mixed organocopper reagents. Part 4: a kinetic study of group transfer selectivity in C?C coupling of mixed diorganocuprates

The competitive rate data and Taft relationships for the coupling of bromomagnesium n‐butyl (substituted phenyl) cuprates with alkyl bromides show that selective n‐butyl transfer can be explained by an oxidative addition mechanism. Taft reaction constants also show that the residual group FG‐C₆H₄ in the mixed cuprate n‐Bu(FG‐C₆H₄)CuMgBr changes the ability of the copper nucleophile to react with the electrophile RBr. These results provide support for the commonly accepted hypothesis regarding the dependence of the R¹ group transfer ability on the strength of R²? Cu bond in reactions of R¹R²CuMgBr reagents. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermochemistry,bond energies and internal rotor barriers of methyl sulfinic acid,methyl sulfinic acid ester and their radicals

Sulfur–Oxygen containing hydrocarbons are formed in oxidation of sulfides and thiols in the atmosphere, on aerosols and in combustion processes. Understanding their thermochemical properties is important to evaluate their formation and transformation paths. Structures, thermochemical properties, bond energies, and internal rotor potentials of methyl sulfinic acid CH₃S(?O)OH, its methyl ester CH₃S(?O)OCH₃ and radicals corresponding to loss of a hydrogen atom have been studied. Gas phase standard enthalpies of formation and bond energies were calculated using B3LYP/6‐311G (2d, p) individual and CBS‐QB3 composite methods employing work reactions to further improve accuracy of the ${\Delta} _{{\bf f}} H_{{\bf 298}}^{{\bf o}} $ . Molecular structures, vibration frequencies, and internal rotor potentials were calculated. Enthalpies of the parent molecules CH₃S(?O)OH and CH₃S(?O)OCH₃ are evaluated as ?77.4 and ?72.7 kcal mol^?1 at the CBS? QB3 level; Enthalpies of radicals C^?H₂? S(?O)? OH, CH₃? S^?(?O)₂, C^?H₂? S(?O)? OCH₃ and CH₃? S(?O)? OC^?H₂ (CBS‐QB3) are ?25.7, ?52.3, ?22.8, and ?26.8 kcal mol^?1, respectively. The CH₃C(?O)O—H bond dissociation energy is of 77.1 kcal mol^?1. Two of the intermediate radicals are unstable and rapidly dissociate. The CH₃S(?O)? O. radical obtained from the parent CH₃? S(?O)? OH dissociates into methyl radical (${\bf CH}_{{\bf 3}}^{{\bf .}} $ ) plus SO₂ with endothermicity (ΔH_rxn) of only 16.2 kcal mol^?1. The CH₃? S(?O)? OC^?H₂ radical dissociates into CH₃? S^?=O and CH₂=O with little or no barrier and an exothermicity of ?19.9 kcal mol^?1. DFT and the Complete Basis Set‐QB3 enthalpy values are in close agreement; this accord is attributed to use of isodesmic work reactions for the analysis and suggests this combination of B3LYP/work reaction approach is acceptable for larger molecules. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural conformations and electronic interactions of the natural product,oroxylin: a vibrational spectroscopic study

The oroxylin, 5,7‐dihydroxy 6‐methoxy flavone is a potent natural product extracted from ‘Vitex peduncularis’. Density functional theory (DFT) at B3LYP/6‐311G(d,p) level has been used to compute energies of different conformers of oroxylin to find out their stability, the optimized geometry of the most stable conformer and its vibrational spectrum. The conformer ORLN‐1 with torsion angles 0, 180, 180 and 0 degrees, respectively, for H₁₃ O₁₂ C₆ C₅, H₁₄ O₁₀ C₄ C₅, H₁₃ O₁₂ C₆ C₅ and H₁₄ O₁₀ C₄ C₅ is found to be most stable. The optimized geometry reveals that the dihedral angle φ between phenyl ring B and the chrome part of the molecule in − 19.21° is due to the repulsive force due to steric interaction between the ortho‐hydrogen atom H₂₉ of the B ring and H₁₈ of the ring C (H₂₉·H₁₈ = 2.198 Å). A vibrational analysis based on the near‐infrared Fourier transform(NIR‐FT) Raman, Fourier transform‐infrared (FT‐IR) and the computed spectrum reveals that the methoxy group is influenced by the oxygen lone pair‐aryl p_z orbital by back donation. Hence the stretching and bending vibrational modes of the methoxy group possess the lowest wavenumber from the normal values of methyl group. The carbonyl stretching vibrations have been lowered due to conjugation and hydrogen bonding in the molecules. The intramolecular H‐bonding and nonbonded intramolecular interactions shift the band position of O₁₀ H₁₄ and O₁₂ H₁₃ stretching modes, which is justified by DFT results. Copyright © 2008 John Wiley & Sons, Ltd.     

ESR spectroscopics study of radicals formed from methoxycarbonylcholine picrate hemihydrate

Abstract

The electron spin resonance of γ-irradiated single crystals of methoxycarbonylcholine picrate hemihydrate, C₇H₁₆NO₃ ⁺ · C₆H₂N₃O₇ ^? · ½ H₂O has been observed and analyzed for different orientations of the crystal in the magnetic field. The crystals have been investigated between 70 and 350 K. The spectra were found to be temperature independent and the radiation damage centers are attributed to – ?[Obar]OCH₃ and –CH₂CH₂O? radicals. The g and hyperfine coupling constants were found to be almost isotropic with an average, g = 2.0060, a _H1 = 4.4G for –CH₂CH₂O?, g = 2.0050, a _H2 = 3.5G for –CH₂CH₂O? and g = 2.0045, a _H = 3.5 G for –?[Obar]OCH₃. These values indicate a long-range coupling between the unpaired electron and H protons.     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O3PH)(4,4′-bpy)(H2O), Zn(O3PH)(4,4′-bpy)0.5 and Mn[O2PH(C6H5)]2(4,4′-bpy) (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine)

Four novel coordination polymers: Ag(dpa) I, Co(O₃PH)(4,4′-bpy)(H₂O) II, Zn(O₃PH)(4,4′-bpy)_0.5 III and Mn[O₂PH(C₆H₅)]₂(4,4′-bpy) IV (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine), were synthesized by microwave heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21/n with a=11.576(2) Å, b=5.585(2) Å, c=15.243(4) Å, β=109.00(2)°, V=931.8(3) ų. II crystallizes in monoclinic Cc space group with a=22.477(7) Å, b=5.280(1) Å, c=10.404(4) Å, β=96.08(3)°, V=1227.8(7) ų. III crystallizes in monoclinic P21/c space group with a=9.758(2) Å, b=7.449(3) Å, c=10.277(2) Å, β=100.02(2)°, V=735.6(4) ų. IV crystallizes in monoclinic space group P2/c with a=10.174(1) Å, b=11.817(3) Å, c=18.784(4) Å, β=102.14(1)°, V=2207.8(8) ų. I consists of linear metal–metal chains wrapped by dpa ligands. II and III consist of two-dimensional M^II(O₃PH) inorganic sheets cross-linked by 4,4′-bpy ligands, while IV is formed by Mn[O₂PH(C₆H₅)]₂ sheets cross-linked by 4,4′-bpy ligands. I exhibits two-step thermal decomposition at ~200 and ~250°C, resulting in the reduction of Ag⁺ to Ag metal. II loses its coordination water at ~100°C, leaving vacant coordination sites at Co²⁺ ions, while the original framework remains intact. The removal of 4,4′-bpy in II–IV occurs at elevated temperatures above 250, 200 and 400°C respectively.     

The diphenylphosphino radical, (C6H5)2˙P

The diphenylphosphino radical, (C₆H₅)₂P, has been observed at room temperature in X-irradiated single crystals of triphenylphosphine oxide and diphenylphosphine sulphide and in ultra-violet irradiated polycrystalline diphenylphosphine at 77 K. The isotropic ³¹P coupling constant is deduced to be +252 MHz and the anisotropic components are approximately 504, -252, -252 MHz. The largest value of the g tensor lies perpendicularly to the direction of the largest hyperfine coupling constant, the values in diphenylphosphine sulphide being 2·0094, 2·0035 and 2·0021. X-irradiated triphenylphosphine oxide also contains the (C₆H₅)₂PO radical.     

E.P.R. study of γ-irradiated single crystals of K2C2O4.H2O and (NH4)2C2O4.H2O

The electron paramagnetic resonance of γ-irradiated single crystals of K₂C₂O₄.H₂O and (NH₄)₂C₂O₄.H₂O has been studied. The spectra show interesting microwave power saturation effects. The singlet spectrum is attributed to the C₂O₄ ^- radical derived from the C₂O₄ ^-- ion. The principal g-values are determined to be 1·998, 2·0028 and 2·0004. Certain weak lines are observed with different power saturation and interpreted as due to OH radicals derived from water molecules in the crystal lattice.