CH CHCH Research Articles

Hydrogen-Bond Networks: Strengths of Different Types of Hydrogen Bonds and An Alternative to the Low Barrier Hydrogen-Bond Proposal

We report quantifying the strengths of different types of hydrogen bonds in hydrogen-bond networks (HBNs) via measurement of the adiabatic electron detachment energy of the conjugate base of a small covalent polyol model compound (i.e., (HOCH2CH2CH(OH)CH2)2CHOH) in the gas phase and the pKa of the corresponding acid in DMSO. The latter result reveals that the hydrogen bonds to the charged center and those that are one solvation shell further away (i.e., primary and secondary) provide 5.3 and 2.5 pKa units of stabilization per hydrogen bond in DMSO. Computations indicate that these energies increase to 8.4 and 3.9 pKa units in benzene and that the total stabilizations are 16 (DMSO) and 25 (benzene) pKa units. Calculations on a larger linear heptaol (i.e., (HOCH2CH2CH(OH)CH2CH(OH)CH2)2CHOH) reveal that the terminal hydroxyl groups each contribute 0.6 pKa units of stabilization in DMSO and 1.1 pKa units in benzene. All of these results taken together indicate that the presence of a charged center can provide a powerful energetic driving force for enzyme catalysis and conformational changes such as in protein folding due to multiple hydrogen bonds in a HBN.

Rhodium and Iridium Complexes with a New Scorpionate Phosphane Ligand

A straightforward synthesis of a new hybrid scorpionate ligand [(allyl)2B(CH2PPh2)(Pz)](-) ([A2BPN](-)) is reported. Coordination to rhodium resulted in square-planar complexes [Rh(κ(2)-A2BPN)(L)(L')] [L = L' = (1)/2cod (1,5-cyclooctadiene), CN(t)Bu, CO (6); L = CO, L' = NH3, pyridine, PPh3, PMe3] for which spectroscopic data and the molecular structure of [Rh(κ(2)-A2BPN)(CO)PPh3] (11) indicate the ligand to be κN,κP-bound to rhodium with two dangling free allyl groups. Studies in solution point out that the six-membered Rh-N-N-B-C- P metallacycle undergoes a fast inversion in all of them. The bis(carbonyl) complex 6 easily loses a CO group to give [{Rh(A2BPN)(CO)}2], a dinuclear compound in which two mononuclear subunits are brought together by two bridging allyl groups. Coordination to iridium is dominated by a tripodal κN,κP,η(2)-C═C binding mode in the TBPY-5 complexes [Ir(κ(3)-A2BPN)(L)(L')] [L = L' = (1)/2cod (3), CN(t)Bu (5), CO (7); L = CO, L' = PPh3 (13), PMe3 (14), H2C═CH2, (17), MeO2CC≡CCO2Me (dmad, 18)], as confirmed by the single-crystal structure determination of complexes 3 and 18. A fast exchange between the two allyl arms is observed for complexes having L = L' (3, 5, and 7), while those having CO and L ligands (14, 17, and 18) were found to be nonfluxional species. An exception is complex 13, which establishes an equilibrium with the SP-4 configuration. Protonation reactions on complexes 13 and 14 with HCl yielded the hydride complex [Ir(κ(2)-A2BPN)(CO)(Cl)(H)PPh3] (15) and the C-alkyl compound [ Ir{κ(3)-(allyl)B(CH2 CHCH3)(CH2PPh2)(Pz)}(Cl)(CO)PMe3] (16), respectively. The bis(isocyanide) complex 5 reacts with dmad to form [Ir(κ(2)-A2BPN)(CN(t)Bu)2(dmad)]. On the whole, the electronic density provided to the metal by the [A2BPN](-) ligand is very sensitive to the coordination mode. The basicity of the new ligand is similar to that of the Tp(Me2) ligand in the κN,κP mode but comparable to Tp if coordinated in the κN,κP,η(2)-C═C mode.

Haloboration of internal alkynes with boronium and borenium cations as a route to tetrasubstituted alkenes.

Hail boration! 2-Dimethylaminopyridine-ligated dihaloborocations [X2B(2-DMAP)](+) with a strained four-membered boracycle were used for the haloboration of terminal and dialkyl internal alkynes (see scheme). Esterification then provided vinyl boronate esters as useful precursors to tetrasubstituted alkenes. Following mechanistic studies, the scope of the haloboration was expanded simply by variation of the amine. Pin = 2,3-dimethyl-2,3-butanedioxy.

Synthesis, X-ray Characterization, and Reactivity of α-Aminoacidato Ethoxide Complexes of Niobium(V) and Tantalum(V)

High yields of the ethoxo-α-aminoacidates of the general formula M(OEt)4[OC(O)CHRNHR'-κO,κN] (M = Nb, R = CH2Ph, R' = H, 2; R = CHMe2, R' = H, 3; R = CH2CHMe2, R' = H, 4; R = H, R' = Me, 5; R = CH2CH2SMe, R' = H, 6; M = Ta, R = CH2Ph, R' = H, 7; R = CH2CH2SMe, R' = H, 8) and M(OEt)4(OC(O)CH(CH2CH2CH2)NH-κO,κN) (M = Nb, 9; Ta, 10) have been obtained by the reaction of the l-enantiopure α-amino acid (or sarcosine) with a slight molar excess of M(OEt)5 (M = Nb, 1a; Ta, 1b) in a dichloromethane solution. The new complexes 2-10 have been fully characterized by spectroscopic and analytical methods and by X-ray diffraction for 2 and 7-9. Such X-ray structures are the first ones ever reported for niobium and tantalum coordination compounds containing an α-aminoacidato ligand. The early-late heterobimetallic derivative Ta(OEt)4[O2CCH(NH2)CH2CH2S(CH3)(AuCl)] (11) has been prepared by the reaction of 8 with a stoichiometric amount of Au(CO)Cl. The bulk polymerization of D,L-lactide initiated by complexes 2 and 7 gave a slightly heterotactic enchainment (Pr = 0.54 and 0.63, respectively), whereas complexes 1a and 1b formed fully atactic polylactide with P(r) ≈ 0.4.

Application of vegetable oils for electrocatalytic synthesis of hydrocarbons

Conditions of Kolbe cross-electrosynthesis of 10-undecylenic and acetic acids are studied on different catalyst anodes. It is shown that the key anodic process stages are the stages of formation of vinyl radicals from anions of unsaturated and methyl radicals under electrosynthesis of acetate anions. As dependent on the conditions of the process, the main product formed on the anode of the Pt-10% Ir alloy is either hydrocarbon CH3CH2CH(CH3)(CH2)7CH2CH3 (58 wt %) being the product of addition of three methyl radicals to a vinyl radicals or olefin CH2=CH(CH2)7CH2CH3 (57 wt %) being the product of dimerization of vinyl and methyl radicals.

The soft X-ray absorption spectrum of the allyl free radical

The first experimental study of the X-ray absorption spectrum (XAS) of the allyl free radical, CH(2)CHCH(2), is reported. A supersonic He seeded beam of hyperthermal allyl radicals was crossed by a high resolution synchrotron radiation (SR) in the focus of a 3D ion momentum imaging time-of-flight (TOF) spectrometer to investigate the soft X-ray absorption and fragmentation processes. The XAS, recorded as Total-Ion-Yield (TIY), is dominated by C1s electron excitations from either the central carbon atom, C(C), or the two terminal carbon atoms, C(T), to the frontier orbitals, the semi-occupied-molecular-orbital (SOMO) and the lowest-unoccupied-molecular-orbital (LUMO). All of the intense features in the XAS could only be assigned with the aid of ab initio spectral simulation at the Multi-Configuration Self-Consistent-Field (MCSCF) level of theory, this level being required because of the multi-reference nature of the core-excited state wavefunctions of the open shell molecule. The ionization energies (IEs) of the singlet and triplet states of the C1s ionized allyl radical (XPS) were also calculated at the MCSCF level.

Hyperbranched polycarbosiloxanes and polycarbosilanes via bimolecular non-linear hydrosilylation polymerization

The syntheses and selected structure–property relationships of two series of polycarbosiloxanes (HB-PCSOX) and polycarbosilanes (HB-PCS) prepared by the platinum-catalyzed bimolecular non-linear hydrosilylation polymerizations of commercially available 1,3-diallyl- or 1,3-divinyl- disiloxanes or disilanes and tri- or tetra-functional siloxysilanes or silanes (i.e., Ax + By polymerization systems where x = 2 and y = 3 or 4) are described. The polymerizations were controlled to avoid gelation and ensure preparation of non-crosslinked soluble polymer products by adjusting the molar ratios of the reacting A (allylsilyl, Si–CH2–CHCH2, or vinylsilyl, Si–CHCH2) and B (silyl, Si–H) reactive functional groups such that r ≤ 1/[(x − 1)(y − 1)] or r ≥ (x − 1)(y − 1) where r = [A]/[B]. The polymers were characterized by IR, 1H, 13C and 29Si NMR, SEC, DSC and TGA. Their molecular weights were found to increase in the following order of the side-group substitution in the 1,3-divinyldisiloxane monomer used: EtO > Me > MePh > Ph2, consistent with the increased electron-donation to the vinyl groups causing their increased reactivity in hydrosilylation. These polymers represent unique yet easily and economically available multifunctional nanoscopic dendritic building blocks for more complex 3D nano-structured materials for a variety of applications in electronics, photonics, lithography, specialty coatings, etc.

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H(2)) were investigated with infrared (IR) absorption spectra. When a p-H(2) matrix containing Cl(2) and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm(-1), and several weaker ones due to the trans-1-chloromethylallyl radical, ●(CH(2)CHCH)CH(2)Cl, appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the Cl atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of Cl + propene in solid p-H(2) [J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)] in which the addition of Cl to the central C atom is favored, likely through steric effects in a p-H(2) matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm(-1), were observed when the UV-irradiated Cl(2)/trans-1,3-butadiene/p-H(2) matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, ●(CH(2)CHCH)CH(3), produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of Cl atoms with solid p-H(2) exposed to IR radiation.

Synthesis of trans‐Disubstituted Alkenes by Cobalt‐Catalyzed Reductive Coupling of Terminal Alkynes with Activated Alkenes

A cobalt-catalyzed reductive coupling of terminal alkynes, RC≡CH, with activated alkenes, R'CH=CH(2), in the presence of zinc and water to give functionalized trans-disubstituted alkenes, RCH=CHCH(2)CH(2)R', is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl(2)/P(OMe)(3)/Zn catalyst system to afford 1,2-trans-disubstituted alkenes with high regio- and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl(2)/P(OPh)(3)/Zn system providing a mixture of 1,2-trans- and 1,1-disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3-enynes and acetylene gas with alkenes. Furthermore, a phosphine-free cobalt-catalyzed reductive coupling of terminal alkynes with enones, affording 1,2-trans-disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air-stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed.

Reaction of Phenyl Radical with Propylene as a Possible Source of Indene and Other Polycyclic Aromatic Hydrocarbons: An Ab Initio/RRKM-ME Study

Ab initio G3(MP2,CC)//B3LYP/6-311G** calculations have been performed to investigate the potential energy surface (PES) and mechanism of the reaction of phenyl radical with propylene followed by kinetic RRKM-ME calculations of rate constants and product branching ratios at various temperatures and pressures. The reaction can proceed either by direct hydrogen abstraction producing benzene and three C(3)H(5) radicals [1-propenyl (CH(3)CHCH), 2-propenyl (CH(3)CCH(2)), and allyl (CH(2)CHCH(2))] or by addition of phenyl to the CH or CH(2) units of propylene followed by rearrangements on the C(9)H(11) PES producing nine different products after H or CH(3) losses. The H abstraction channels are found to be kinetically preferable at temperatures relevant to combustion and to contribute 55-75% to the total product yield in the 1000-2000 K temperature range, with the allyl radical being the major product (~45%). The relative contributions of phenyl addition channels are calculated to be ~35% at 1000 K, decreasing to ~15% at 2000 K, with styrene + CH(3) and 3-phenylpropene + H being the major products. Collisional stabilization of C(6)H(5) + C(3)H(6) addition complexes is computed to be significant only at temperatures up to 1000-1200 K, depending on the pressure, and maximizes at low temperatures of 300-700 K reaching up to 90% of the total product yield. At T > 1200 K collisional stabilization becomes negligible, whereas the dissociation products, styrene plus methyl and 3-phenylpropene + H, account for up to 45% of the total product yield. The production of bicyclic aromatic species including indane C(9)H(10) is found to be negligible at all studied conditions indicating that the phenyl addition to propylene cannot be a source of polycyclic aromatic hydrocarbons (PAH) on the C(9)H(11) PES. Alternatively, the formation of a PAH molecule, indene C(9)H(8), can be accomplished through secondary reactions after activation of a major product of the C(6)H(5) + C(3)H(6) addition reaction, 3-phenylpropene, by direct hydrogen abstraction by small radicals, such as H, OH, CH(3), etc. It is shown that at typical combustion temperatures 77-90% of C(9)H(9) radicals formed by H-abstraction from 3-phenylpropene undergo a closure of a cyclopentene ring via low barriers and then lose a hydrogen atom producing indene. This results in 7.0-14.5% yield of indene relative to the initial C(6)H(5) + C(3)H(6) reactants within the 1000-2000 K temperature range.

Stepwise synthesis of a hydrido, N-heterocyclic dicarbene iridium(iii) pincer complex featuring mixed NHC/abnormal NHC ligands

We describe a stepwise synthesis of the hydrido, N-heterocyclic dicarbene iridium(III) pincer complex [Ir(H)I(C(NHC)CC(aNHC))(NCMe)] (3) which features a combination of normal and abnormal NHC ligands. The reaction of the bis(imidazolium) diiodide [(CH(imid)CHCH(imid))]I(2) (1) with [Ir(μ-Cl)(cod)](2) afforded first the mono-NHC Ir(I) complex [IrI(cod)(CH(imid)CHC(NHC))]I (2), which was then reacted with 2 equiv. of Cs(2)CO(3) in acetonitrile at 60 °C for 40 h to yield 3. These observations support our previously proposed mechanism for the formation of hydrido, N-heterocyclic dicarbene iridium(III) pincer complexes from the reaction of bis(imidazolium) salts with weak bases involving a mono-NHC Ir(I) intermediate. We describe the reactivity of the mono-NHC Ir(I) complex 2 under various conditions. By changing the reaction solvent from MeCN to toluene, we observed the cleavage of the imidazol-2-ylidene ring and the formation of an iminoformamide-containing mono-NHC Ir(I) complex [IrI(cod){[NHCH=CHN(Ad)CHO]CHC(NHC)}] (4). Complex 4 was also prepared in high yield from the reaction of 2 with strong bases (potassium tert-butoxide or potassium hexamethyldisilazane), via the initial formation of the complex [IrI(cod)(CH(NHC)CHC(NHC))] (5), which contains a coordinated NHC moiety and a free carbene arm, followed by subsequent hydrolysis of the latter. The bis(imidazolium) salt 1 can be deprotonated by strong bases to form the bis(carbene) ligand C(NHC)CHC(NHC) (6), which readily reacts with [Ir(μ-Cl)(cod)](2) to give the dinuclear complex [{IrI(cod)}(2)(μ-C(NHC)CHC(NHC))] (7), in which the N-heterocyclic bis(carbene) ligand bridges the two metals through the carbene carbon atoms.

Theoretical study on the mechanism for the reaction of F with CH 2CHCH 2Cl

The complex potential energy surfaces for the reaction of atomic radical F with CH 2CHCH 2Cl (3-chloropropene) are explored at the CCSD(T)/cc-pVTZ//MP2(full)/6-311++G(d,p) level. There are various possible reaction pathways including the addition–elimination and H-abstraction reaction. Among them, the most feasible pathway should be to produce P1 (CH 2CHCH 2F + Cl), which is in good agreement with the experiment. Among the H-abstraction reactions, the most competitive pathway is the atomic radical F abstracting hydrogen atom from allylic group. Because all of the transition states and intermediates involved in the title reaction lie below the reactants, the F + CH 2CHCH 2Cl reaction is expected to be rapid. The present results could lead us to deeply understand the mechanism of the title reaction and may provide some useful information for future experimental investigation of the title reaction.

Photochemistry and Photophysics of n-Butanal, 3-Methylbutanal, and 3,3-Dimethylbutanal: Experimental and Theoretical Study

Dilute mixtures of n-butanal, 3-methylbutanal, and 3,3-dimethylbutanal in synthetic air, different N(2)/O(2) mixtures, and pure nitrogen (up to 100 ppm) were photolyzed with fluorescent UV lamps (275-380 nm) at 298 K. The main photooxidation products were ethene (n-butanal), propene (3-methylbutanal) or i-butene (3,3-dimethylbutanal), CO, vinylalcohol, and ethanal. The photolysis rates and the absolute quantum yields were found to be dependent on the total pressure of synthetic air but not of nitrogen. At 100 Torr, the total quantum yield Φ(100) = 0.45 ± 0.01 and 0.49 ± 0.07, whereas at 700 Torr, Φ(700) = 0.31 ± 0.01 and 0.36 ± 0.03 for 3-methylbutanal and 3,3-dimethybutanal, respectively. Quantum yield values for n-butanal were reported earlier by Tadić et al. (J. Photochem. Photobiol. A2001143, 169-179) to be Φ(100) = 0.48 ± 0.02 and Φ(700) = 0.32 ± 0.01. Two decomposition channels were identified: the radical channel RCHO → R + HCO (Norrish type I) and the molecular channel CH(3)CH(CH(3))CH(2)CHO → CH(2)CHCH(3) + CH(2)═CHOH or CH(3)C(CH(3))(2)CH(2)CHO → CHC(CH(3))CH(3) + CH(2)═CHOH, (Norrish type II) having the absolute quantum yields of 0.123 and 0.119 for 3-methybutanal and 0.071 and 0.199 for 3,3-dimethylbutanal at 700 Torr of synthetic air. The product ethenol CH(2)═CHOH tautomerizes to ethanal. We have performed ab initio and density functional quantum (DFT) chemical computations of both type I and type II processes starting from the singlet and triplet excited states. We conclude that the Norrish type I dissociation produces radicals from both singlet and triplet excited states, while Norrish type II dissociation is a two-step process starting from the triplet excited state, but is a concerted process from the singlet state.

Cationic Ethylzinc Compound: A Benzene Complex with Catalytic Activity in Hydroamination and Hydrosilylation Reactions

The tight ion pair [EtZn(η(3)-C(6)H(6))][CHB(11)Cl(11)]·C(6)H(6) (1·C(6)H(6)) was obtained through β-hydrogen abstraction and concomitant ethene elimination from Et(2)Zn with the trityl salt [Ph(3)C][CHB(11)Cl(11)]. This ionlike species shows catalytic activity in hydrosilylation and intramolecular hydroamination reactions. The amine adduct {CH(2)CHCH(2)C(Ph(2))CH(2)NH(2)}(3)ZnCB(11)Cl(11) (3), which features a rare transition metal-carborane σ bond, was isolated from a hydroamination experiment.

Synthesis and Coordination Chemistry ofN,N-Diallylbispidine

The synthesis of 3,7-diallyl-3,7-diazabicyclo[3.3.1]nonane (C7H12N2allyl2, 3) has been revisited, and several hitherto undetected byproducts have been identified. Pure 3 and these byproducts were isolated by both prep-GC and column chromatography. Monoprotonated 3 in the form of the PF6 salt [(C7H13N2allyl2]PF6 (9) and the addition complexes of 3 to Ni(acac)2 and CuI, (C7H12N2allyl2)Ni(acac)2 (10) and {(C7H12N2allyl2)Cu(μ-I)}2 (11), have been prepared. From the reactions of {(η3-C3H5)M(μ-X)}2 (M = Ni, Pd, Pt; X = Cl, Br) with 3 and TlPF6 the complexes [(C7H12N2allyl2)M(η3-C3H5)]PF6 (M = Ni (12a), Pd (12b), Pt (12c)) were obtained. Compounds 9–11 and 12b were characterized by X-ray crystallography. The reaction of (1,5-hexadiene)PtCl2 with 3 gave, after HCl elimination, monomeric {C7H12N2(C3H5)CH═CHCH2}PtCl (13a), and the presence of MeOH afforded {C7H12N2(C3H5)CH2CH(OMe)CH2}PtCl (13b), both compounds featuring novel anionic tridentate ligands. Furthermore, chiral N,N′-bis((R)-1-phenylethyl)-1,7-octadiene-(S,S)-4,5-diamine (15) reacts with CuI to give [{(C3H5)2C2H4N2(CHMePh)2}Cu(μ-I)]2 (16). The unbound N-allyl functions on the ligands in the product complexes allow for immobilization of the transition metal complexes on polyester fibers.

Characterization of iron(III) oxide/hydroxide nanostructured materials produced by sol–gel technology based on the Fe(NO 3) 3·9H 2O–C 2H 5OH–CH 3CHCH 2O system

Nanostructured iron oxide/hydroxide materials were synthesized by sol–gel technology, starting from the ternary system Fe(NO 3) 3·9H 2O/ethanol/propylene oxide. Evaporative drying and supercritical fluids extraction were used as drying techniques to produce xerogels and aerogels, respectively. The materials were physically, structurally and chemically characterized, to analyze their suitability for surface-dependent applications and the influence of the drying technique on their properties. In addition, the chemistry involved in the sol–gel synthesis of iron oxides/hydroxides with the referred ternary system is reviewed. The produced materials were composed by aggregates of nanometric crystallites: ∼1 nm for xerogels and ∼5 nm for aerogels. Their high porosity and surface area (xerogels – 50% and 150 m 2 g −1; aerogels – 90% and 400 m 2 g −1) make them suitable for surface-dependent processes, being the aerogels far more adequate. The FTIR, XRD and Mössbauer spectroscopy results gave some insight on the composition of these materials, showing that the 2-line ferrihydrite is their most probable constituent phase. Finally, it was concluded that the continuous supercritical fluids extraction is the best drying procedure for these materials, since it preserves the mesoporous structure of the gels. When evaporative drying is used, the pores shrinkage leads to a predominantly microporous structure.

Synthesis and Properties of Novel Double‐Tail Trisiloxane Surfactants with High Spreading Ability

AbstractA new type of double‐tail trisiloxane surfactants of the general formula R1NR2CH2CH(OH)CH2O(CH2CH2O)xCH3 (x = 8.4, 12.9, 17.5, 22; R1 = Me3SiOSiMe(CH2)3OSiMe3, R2 = CH2CH(OH)CH2OR3, R3 = CH2CH(C2H5)CH2(CH2)2CH3) has been synthesized by reacting single‐tail trisiloxane surfactants with 2‐ethylhexyl glycidyl ether. Their structures were characterized with 1H‐NMR and 13C‐NMR spectroscopy. These double‐tail trisiloxane surfactants reduce the surface tension of water to less than 24 mN/m at a level of 10−5 mol/L. The spreading ability (SA) of the double‐tail trisiloxane surfactant solution on Parafilm (or Ficus microcarpa leaf) surfaces is better than that on polyethylene terephthalate surface. The SA of the solution of the double‐tail trisiloxane surfactants 1J with average ethoxy units of 8.4 is far better than the others, and its solution (5.0 × 10−3 mol/L) possesses an SA value of over 15 within 10 min on Parafilm and Ficus microcarpa leaf surfaces. The surface tension values of aqueous solutions (1.0 × 10−3 mol/L) of the double‐tail trisiloxane surfactants 1J are still less than 25 mN/m over 21 days in an acidic environment (pH 4.0) and 139 days in an alkaline environment (pH 10.0), respectively. It is suggested that the SA and hydrolysis resistance of double‐tail trisiloxane surfactants are able to be improved by changing the structure of the hydrophobic group, such as increasing the molar ratio of methyl to methylene.

Theoretical study on the mechanism for the reaction of OH with CH 2[dbnd]CHCH(OH)CH 3

The detailed potential energy surface for the key atmospheric reaction of OH with CH 2 CHCH(OH)CH 3 (3-buten-2-ol) has been investigated at the CCSD(T)/6-311++G(d,p)//MP2(full)/6-311++G(d,p) level. Various possible H-abstraction and addition–elimination pathways are identified. It is predicted that the formation of intermediates c1 ( CH 2CH(OH)CH(OH)CH 3) in the addition process via pre-reactive complex a3 is more favorable than that of the H-abstraction reactions at low temperature. Starting from c1, the most feasible pathway is the formation of P7 (CH 2 CHOH(I) + CH 3 CHOH(I)) by directly C C bond rupture or formation of P14 (CH 3CHO + CH 3 CHOH(I)) via isomerization/dissociation mechanisms, all of which have comparable contributions to the title reaction. P14 (CH 3CHO + CH 3 CHOH(I)) are the dominate products. In the H-abstraction pathways, the dominant channel is the allylic H atom abstraction leading to P5 (CH 2 CH C(OH)CH 3) + H 2O, which may play an important role at higher temperature. The other pathways are less significant due to higher barrier height and unstable product. This calculation is useful to simulate to guide experimental investigations of the title reaction.

The Dynamics of Allyl Radical Dissociation

Dissociation of the allyl radical, CH(2)CHCH(2), and its deuterated isotopolog, CH(2)CDCH(2), have been investigated using trajectory calculations on an ab initio ground-state potential energy surface calculated for 97,418 geometries at the coupled cluster single and double and perturbative treatment of triple excitations, with the augmented correlation consistent triple-ζ basis set level (CCSD(T)/AVTZ). At an excitation energy of 115 kcal/mol, corresponding to optical excitation at 248 nm, the primary channel is hydrogen loss with a quantum yield of 0.94 to give either allene or propyne in a ratio of 6.4:1. The total dissociation rate for CH(2)CHCH(2) is 6.3 × 10(10) s(-1), corresponding to a 1/e time of 16 ps. Methyl and C(2)H(2) are produced with a quantum yield of 0.06 by three different mechanisms: a 1,3 hydrogen shift followed by C-C cleavage to give methyl and acetylene, a double 1,2 shift followed by C-C cleavage to give methyl and acetylene, or a single 1,2 hydrogen shift followed by C-C cleavage to give methyl and vinylidene. In this last channel, the vinylidene eventually isomerizes to give internally excited acetylene, and the kinetic energy distribution is peaked at much lower energy (6.4 kcal/mol) than that for the other two channels (18 kcal/mol). The trajectory results also predict the v-J correlation, the anisotropy of dissociation, and distributions for the angular momentum of the fragments. The v-J correlation for the CH(3) + HCCH channel is strongest for high rotational levels of acetylene, where v is perpendicular to J. Methyl elimination is anisotropic, with β = 0.66, whereas hydrogen elimination is nearly isotropic. In the hydrogen elimination channel, allene is rotationally excited with a total angular momentum distribution peaked near J = 17. In the methyl elimination channel, the peak of the methyl rotational distribution is at J ≈ 12, whereas the peak of the acetylene rotational distribution is at J ≈ 28.

Infrared and Raman spectral data and conformations of 1-pentyne

The infrared spectra of 1-pentyne (CH 3CH 2CH 2 C CH) have been studied as a vapour and as a crystalline solid at 78 K. Raman spectra of the liquid were recorded at 293 K and polarization data were obtained. Additional Raman spectra of the liquid were recorded at various temperatures between 295 and 183 K. Several Raman bands vanished in the low temperature solid at 160 K, and both the IR and Raman spectra revealed that only one conformer was present in the crystal lattice. The compound exists a priori in two conformers, anti and gauche, and from bands belonging to these conformers, treated as peak heights or integrated areas at variable temperatures, a value of Δ H equal to 0.75 kJ mol −1 was found in the neat liquid, leading to 59% of the gauche conformer at room temperature. Below freezing temperatures, anti was the only conformer present in the crystal lattice. The observed vibrational spectra were interpreted, supported by previous calculations and in good agreement with earlier studies.