Vinyl CH Research Articles

Mechanistic study of heterogeneous propene metathesis on WOx/SiO2 catalysts

Silica-supported tungsten oxides are widely used industrial catalysts for olefin metathesis due to their low cost and robustness, yet the mechanisms for heterogeneously catalyzed metathesis reactions remain comparatively less understood. In this work, density-functional theory (DFT) calculations were used to study the model reactions of propene metathesis. Our calculations confirm that the metathesis reactions catalyzed by WOx/SiO2 largely follow the Chauvin cycle, with an overall energetic barrier of 142 kJ/mol. To understand how the initial alkylidene active sites are generated, three mechanisms were examined: The pseudo-Wittig mechanism was found to be most favorable and proceeds with a metallacycle intermediate, while the allylic and vinylic CH activations are much more difficult and require the reduction of surface sites to W(+4). Relative to the adsorbed reactant state, the overall intrinsic barriers for three mechanisms were computed to be 193, 261, and 355 kJ/mol, respectively. The higher barriers for active-site formation than for the metathesis cycle are consistent with the difficult, high-temperature pretreatment required in experiments to activate WOx/SiO2 catalysts.

Investigation of cyclohexene thermal decomposition and cyclohexene + OH reactions

Cyclohexene is a common intermediate in the oxidation of cyclohexane and alkyl-substituted cyclohexanes. It also plays an important role in the formation of polycyclic aromatic hydrocarbons (PAHs) by providing a route for the first aromatic ring. Two types of reactions are highly important in cyclohexene kinetics, i.e., H-abstraction by OH radicals and cyclohexene thermal decomposition. In this work, we have investigated these two reactions experimentally by employing sensitive UV diagnostics of OH radicals and 1,3-butadiene. We conducted rate coefficient measurements of cyclohexene + OH reaction (k1) over 933–1259 K and 1–4 bar using a narrow-linewidth UV absorption diagnostic of OH radicals near 306.67 nm. The carefully designed test conditions minimized the influence of secondary reactions such as cyclohexene thermal decomposition. Our determined OH + cyclohexene high-temperature rate coefficients show a positive temperature dependence and a negligible pressure dependence. Our rate values may be fitted with a two-parameter Arrhenius expression (units of cm3molecule−1s−1):k1=1.28×10−10e(−1225T)We also investigated channel-specific competition in OH + cyclohexene reaction. H-abstraction by OH from allylic (kc), alkylic (kb), and vinylic (ka) CH bonds contributes roughly 60%, 35%, and 5% over our temperature range. Our determined kc agrees excellently with literature rate coefficient of H-abstraction from the allylic site of 1-butene.We studied cyclohexene thermal decomposition reaction (k2) by tracing the product 1,3-butadiene near 212.5 nm over 1092–1361 K and 0.82–1 bar. Compared to literature works, our highly sensitive UV diagnostic of 1,3-butadiene enabled time-resolved measurements with low cyclohexene concentration, which guaranteed nearly isothermal conditions despite reaction endothermcity. Our measured rate coefficients may be expressed as (unit of s−1):k2=3.68×1014e(−31,562T)We implemented our determined rate coefficients (k1 and k2) in a literature cyclohexene kinetic model and also updated the 1,3-butadiene sub-mechanism. The updated model shows improved predictions of measured ignition delay times of cyclohexene.

1,3-Dibromo-5, 5-dimethylhydantoin (DBDMH)-promoted cross-coupling of enaminones with phenols under metal-free conditions

Despite significant progress in the area of enaminone vinyl CH functionalization, approaches for the direct synthesis of phenoxyl enaminone molecules remain a challenge. Here we describe a highly efficient 1,3‑Dibromo 5,5-dimethylhydantoin (DBDMH)-promoted cross-coupling reaction between enaminones and phenols. This method provides straightforward access to a wide range of polyfunctionalized aminophenoxyalkenes under mild conditions. The main advantageous features of this method includes a wide substrate scope and good functional group tolerance, operational simplicity, and easily available starting materials.

Unraveling Conformer-Specific Sources of Hydroxyl Radical Production from an Isoprene-Derived Criegee Intermediate by Deuteration.

Ozonolysis of isoprene, the most abundant volatile organic compounds emitted into the Earth's troposphere after methane, yields three distinct Criegee intermediates. Among these, methyl vinyl ketone oxide (MVK-oxide) is predicted to be the major source of atmospheric hydroxyl radicals (OH) from isoprene ozonolysis. Previously, Barber et al. [ J. Am. Chem. Soc., 2018, 140, pp 10866-10880] demonstrated that syn-MVK-oxide conformers undergo unimolecular decay via 1,4-hydrogen (H) transfer from the methyl group to the adjacent terminal oxygen atom, followed by the prompt release of OH radical products. Here, we selectively deuterate the methyl group of MVK-oxide (d3-MVK-oxide) and record its IR action spectrum in the vinyl CH stretch overtone (2νCH) region. The resultant time-dependent appearance of OD radical products, detected by laser-induced fluorescence, demonstrates that a unimolecular decay of d3-MVK-oxide proceeds by an analogous 1,4-deuterium (D) atom transfer mechanism anticipated for syn conformers. The experimental spectral and temporal results are compared with the calculated IR absorption spectrum and unimolecular decay rates predicted by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory for syn-d3-MVK-oxide, as well as the prior study on syn-MVK-oxide. The d3-MVK-oxide IR action spectrum is similar to that for MVK-oxide, yet exhibits notable changes as the overtone and combination transitions involving CD stretch shift to a lower frequency. The unimolecular decay rate for d3-MVK-oxide is predicted to be a factor of 40 times slower than that for MVK-oxide in the 2νCH region. Experimentally, the temporal profile of the OD products reflects the slower unimolecular decay of d3-MVK-oxide compared to that for MVK-oxide to OH products as well as experimental factors. Both experiment and theory demonstrate that quantum mechanical tunneling plays a very important role in the 1,4-H/D-transfer processes at energies in the vicinity of the transition-state barrier. The similarities of the IR action spectra and changes in the unimolecular decay dynamics upon deuteration indicate that syn conformers make the main contribution to the IR action spectra of MVK-oxide and d3-MVK-oxide.

Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction.

Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. This work investigates the reactions of the smallest Criegee intermediate, CH2OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-α (10.2 eV) radiation for photoionization. CH2OO was produced via pulsed laser photolysis of CH2I2 in the presence of excess O2. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH2OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH2OO + MVK) = (5.0 ± 0.4) × 10-13 cm3 s-1 and k(CH2OO + MACR) = (4.4 ± 1.0) × 10-13 cm3 s-1, where the stated ±2σ uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH2OO + CO reaction and for the reaction of CH2OO with CF3CHCH2 at 300 K and 4 Torr. For CH2OO + CO, no reaction is observed and an upper limit is determined: k(CH2OO + CO) < 2 × 10-16 cm3 s-1. For CH2OO + CF3CHCH2, an upper limit of k(CH2OO + CF3CHCH2) < 2 × 10-14 cm3 s-1 is obtained.

Clean and selective catalytic C-H alkylation of alkenes with environmental friendly alcohols

Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science2011, 333, 1613] allow the formation of a CC bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the CO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic CH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments.

Regioselective preferential C[sbnd]H activation of sterically hindered 1,3-dienes over [4+2] cycloaddition

The study of Pd-catalyzed preferential CH activation of sterically hindered α, β-olefinic indoles onto alkenes beyond [4 + 2] cycloaddition has been described. The carbazole derivatives were readily synthesized via activation of vinylic CH bonds with excellent regioselectivity. Further, the one-pot strategy has been employed for the synthesis of tricyclic carbazoles. The double and triple CH activation followed by concomitant Michael addition provides an economical approach for the synthesis of N-protected carbazole. A wide range of alkenes at the α- and β-position are compatible with this reaction. The mechanistic and X-ray crystallographic studies supported the designed chemistry of CH activation.

Novel anion receptors for selective recognition of dimethyl phosphinate and carboxylate

We have designed and synthesized new anion receptors 1 and 2, which have amide NH, pyrrole NH and vinyl CH as hydrogen bond donors. These receptors are selective for dimethyl phosphinate and carboxylates. Due to electron withdrawing effect of the cyano group which is trans to the vinyl hydrogen with respect to carbon-carbon double bond, receptor 1 has higher binding constants for phosphinate and carboxylate than those of receptor 2. Modeling studies shows that cyano group polarized all three hydrogens through planar π-electron network. In addition, receptor 1 gave orange colored 1,4-addition product for cyanide.

Consumption and hydrocarbon growth processes in a 2-methyl-2-butene flame

This paper is concerned with the investigation of the chemical structure of a low-pressure, fuel-rich (ɸ = 1.8) premixed laminar flame fueled with 2-methyl-2-butene employing flame-sampling molecular-beam mass spectrometry with vacuum-ultraviolet single-photon ionization. Partially isomer-resolved mole fraction profiles can be explained by a decomposition scheme based on hydrogen abstraction and addition reactions. The presence of 9 allylic CH bonds compared to only one vinylic CH bond is the key feature that governs the fuel consumption and subsequent hydrocarbon growth reactions. Compared to other alkenes, including e.g., 1-butene, 2-butene, and iso-butene (Schenk et al., 2013), 2-methyl-2-butene shows a remarkable tendency to form soot precursor molecules such as toluene. In particular, experimental evidence is provided here that toluene, o-xylene, and styrene can be a starting point for PAH formation, thus serving as first aromatic rings besides benzene. The formation of toluene, o-xylene, and styrene can be traced back to the reactions of the resonantly stabilized C4H5 [∙CH2CCCH3 and CH2CH∙CCH2] radicals and the C5H7 [CH2C(CH3)∙CCH2] radicals that are readily formed through fuel-specific decomposition channels. Our experimental data in form of mole fraction profiles as a function of height above the burner for a mass range from 2 to 210 u can serve as reliable validation targets for model development. A preliminary comparison to the model of Westbrook et al. [1] that was optimized to capture ignition delay times and the low-temperature oxidation regime, shows promising elements already for the initial fuel consumption.

In vivo H1 MR spectroscopy using 3 Tesla to investigate the metabolic profiles of joint fluids in different types of knee diseases.

In vivo proton (H1) magnetic resonance spectroscopy (MRS) has not yet been systematically used to study joint fluids in human knees. The objective of this study, therefore, was to assess the ability of proton MRS to identify the apparent heterogeneous characteristics of metabolic spectra in the joint fluid regions in human knees using a high‐field MRI system. Eighty‐four patients with effusion lesions who were referred for routine knee MR imaging underwent proton MRS with point‐resolved, single‐voxel MR spectroscopy using a clinical 3.0 Tesla MRI system. Thirty‐eight patients were confirmed to have the following: degenerative osteoarthritis, 21 patients (Group 1); traumatic diseases, 12 patients (Group 2); infectious diseases, 4 patients and an inflammatory disease, 1 patient (Group 3). Spectroscopy data were analyzed using the public jMRUI freeware software to obtain lipid metabolites. Nonparametric statistical comparisons were performed to investigate any differences in metabolites among the three disease groups. The major metabolites were vinylic CH=CH lipids around 5.1−5.5 ppm, CH2 lipids around 1.1−1.5 ppm, and CH3 lipids around 0.7−1.0 ppm. Each patient had either a CH=CH lipid peak, CH2 and CH3 lipid peaks, or all three peaks. There were no significant differences among the three groups for the CH3 (p=0.9019), CH2 (p=0.6406), and CH=CH lipids (p=0.5467) and water (p=0.2853); none of the metabolites could differentiate between any of the three types of diseases. The CH2 lipids in the 38 patients who had confirmed fluid characteristics were significantly correlated with CH3 lipids (rho=0.835, p<0.0001). The ratio of CH3 to CH2 was highest in the degenerative disease. In both the degenerative and traumatic diseases, metabolite peaks of the vinylic CH=CH lipids around 5.1−5.5 ppm and of the sum of the CH2 and CH3 lipids around 0.7−1.5 ppm were observed, but in the infectious disease, only a metabolite peak of the sum of the CH2 and CH3 lipids was detected. Although none of the metabolites could statistically significantly differentiate between the three types of diseases, the different lipid metabolite peaks and their ratios in the three disease groups may give us a hint at the different mechanisms of joint fluids in the infectious, degenerative, and traumatic diseases.PACS number(s): 87.61.Ff, 33.25.+k, 87.14.Cc

Weak Acidity of Vinyl CH Bonds Enhanced by Halogen Substitution

As shown by the rates of proton-deuteron exchange in ethylenes with halogen substituents, the weak acidity of vinyl CH bonds is enhanced by halogen substitution. Relative rates of exchange in basic deuterium oxide reflect the relative acidities. Substitution in the α position has the strongest effect. Less electronegative halogens such as bromine increase the acidity more than does fluorine. The vinyl CH acid strengths correlate closely with the energies of deprotonation of isolated molecules into isolated anions, as computed with the MP2/cc-pVQZ model. The smaller deprotonation energies are associated with the stronger acids. Atomic charges from a natural bond order analysis done with the MP2/aug-cc-pVQZ model show that the negative charge becomes more dispersed in the anions of the stronger acids. Results are given for 13 haloethylenes and for 6 halogen-substituted butadienes, cyclopropenes, and a cyclobutene.

1,4-Metal migration in a Cp*Rh(iii) complex

The reaction of [Cp*RhCl(Ph)(PR3)] (R = Ph or Me) with internal alkynes in the presence of NaBAr(F)4 affords the o-vinylaryl complex with a Rh-(vinyl CH) agostic interaction by way of the alkyne insertion followed by 1,4-rhodium migration, providing the first example of the 1,4-migration of a Rh(III) center.

Molecular Structure upon Compression and Stability toward Oxidation of Langmuir Films of Unsaturated Fatty Acids: A Vibrational Sum Frequency Spectroscopy Study

Vibrational sum frequency spectroscopy (VSFS) has been used to determine the stability toward oxidation in air of a series of unsaturated fatty acids, measuring as a function of time the changes in the chemical structure and conformational order of films spread on a Langmuir trough. The fatty acids studied consisted of a 20-carbon backbone with increasing numbers of cis double bonds in the chain: 11c-eicosenoic acid (20:1 EA, omega-9), 11c,14c-eicosadienoic acid (20:2 EA, omega-6), and 11c,14c,17c-eicosatrienoic acid (20:3 EA, omega-3). Measurements at constant surface pressure show that double bonds are lost from the surface region and that drops in intensity of the vinyl CH stretch are detectable within a few minutes of spreading the monolayer. The results are consistent with the fatty acid peroxidation free radical mechanism. The sum frequency spectra also reveal that what remains on the surface is conformationally more disordered with a larger number of gauche defects. The oxidation kinetics are found to be strongly dependent on the packing density of the monolayer, being more stable at higher pressures. Oxidation can be avoided by purging the system in an inert atmosphere. Finally, the molecular structure upon compression was tracked in unoxidized monolayers. The results suggest that the packing and orientation of the double bond sections of all three unsaturated fatty acids show remarkable similarities, with the direction of the double bonds approximately parallel to each other irrespective of the number of unsaturations in the chain, with the 20:3 EA probably forming "iron-angle" structures. The possibility of unsaturated chains in a "hairpin" configuration is discarded for area per molecules smaller than approximately 50 A(2), which corresponds to the lowest surface pressure measured with VSFS.

Phospholipid Monolayers Probed by Vibrational Sum Frequency Spectroscopy: Instability of Unsaturated Phospholipids

The surface specific technique vibrational sum frequency spectroscopy has been applied to in situ studies of the degradation of Langmuir monolayers of 1,2-diacyl-phosphocholines with various degrees of unsaturation in the aliphatic chains. To monitor the degradation of the phospholipids, the time-dependent change of the monolayer area at constant surface pressure and the sum frequency intensity of the vinyl CH stretch at the carbon-carbon double bonds were measured. The data show a rapid degradation of monolayers of phospholipids carrying unsaturated aliphatic chains compared to the stable lipids carrying fully saturated chains when exposed to the ambient laboratory air. In addition, the degradation of the phospholipids can be inhibited by purging the ambient air with nitrogen. This instability may be attributed to spontaneous degradation by oxidation mediated by various reactive species in the air. To further elucidate the process of lipid oxidation in biological membranes artificial Langmuir monolayers probed by a surface specific spectroscopic technique as in this study can serve as a model system for studying the degradation/oxidation of cell membrane constituents.

A para-Hydrogen Investigation of Palladium-Catalyzed Alkyne Hydrogenation

The complexes [Pd(bcope)(OTf)2] (1a), where bcope is (C8H14)PCH2-CH2P(C8H14), and [Pd(tbucope)(OTf)2] (1b), where tbucope is (C8H14)PC6H4CH2P(tBu)2, catalyze the conversion of diphenylacetylene to cis- and trans-stilbene and 1,2-diphenylethane. When this reaction was studied with para-hydrogen, the characterization of [Pd(bcope)(CHPhCH2Ph)](OTf) (2a) and [Pd(tbucope)(CHPhCH2Ph)](OTf) (2b) was achieved. Magnetization transfer from the alpha-H of the CHPhCH2Ph ligands in these species proceeds into trans-stilbene. This process has a rate constant of 0.53 s-1 at 300 K in methanol-d4 for 2a, where DeltaH = 42 +/- 9 kJ mol-1 and DeltaS = -107 +/- 31 J mol-1 K-1, but in CD2Cl2 the corresponding rate constant is 0.18 s-1, with DeltaH = 79 +/- 7 kJ mol-1 and DeltaS = 5 +/- 24 J mol-1 K-1. The analogous process for 2b was too fast to monitor in methanol, but in CD2Cl2 the rate constant for trans-stilbene formation is 1.04 s-1 at 300 K, with DeltaH = 94 +/- 6 kJ mol-1 and DeltaS = 69 +/- 22 J mol-1 K-1. Magnetization transfer from one of the two inequivalent beta-H sites of the CHPhCH2Ph moiety proceeds into trans-stilbene, while the other site shows transfer into H2 or, to a lesser extent, cis-stilbene in CD2Cl2, but in methanol it proceeds into the vinyl cations [Pd(bcope)(CPh=CHPh)(MeOD)](OTf) (3a) and [Pd(tbucope)(CPh=CHPh)(MeOD)](OTf) (3b). When the same magnetization transfer processes are monitored for 1a in methanol-d4 containing 5 microL of pyridine, transfer into trans-stilbene is observed for two sites of the alkyl, but the third proton now becomes a hydride ligand in [Pd(bcope)(H)(pyridine)](OTf) (5a) or a vinyl proton in [Pd(bcope)(CPh=CHPh)(pyridine)](OTf) (4a). For 1b, under the same conditions, two isomers of [Pd(tbucope)(H)(pyridine)](OTf) (5b and 5b') and the neutral dihydride [Pd(tbucope)(H)2] (7) are detected. The single vinylic CH proton in 3 and the hydride ligands in 4 and 5 appear as strong emission signals in the corresponding 1H NMR spectra.

Oligomerization and hydroamination of terminal alkynes promoted by the cationic organoactinide compound [(Et2N)3U][BPh4

The three ancillary amido moieties in the cationic complex [(Et2N)3U][BPh4] are highly reactive and are easily replaced when the complex is treated with primary amines. The reaction of [(Et2N)3U][BPh4] with excess tBuNH2 allows the formation of the cationic complex [(tBuNH2)3(tBuNH)3U][BPh4]. X-ray diffraction studies on the complex indicate that three amido and three amine ligands are arranged around the cationic metal center in a slightly distorted octahedral mer geometry. The cationic complex reacts with primary alkynes in the presence of external primary amines to primarily afford the unexpected cis dimer and, in some cases, the hydroamination products are obtained concomitantly. The formation of the cis dimer is the result of an envelope isomerization through a metal-cyclopropyl cationic complex. In the reaction of the bulkier alkyne tBuC identical to CH with the cationic uranium complex in the presence of various primary amines, the cis dimer, one trimer, and one tetramer are obtained regioselectively, as confirmed by deuterium labeling experiments. The trimer and the tetramer correspond to consecutive insertions of an alkyne molecule into the vinylic CH bond trans to the bulky tert-butyl group. The reaction of (TMS) C identical to CH with the uranium catalyst in the presence of EtNH2 followed a different course and produced the gem dimer along with the hydroamination imine as the major product. However, when other bulkier amines were used (iPrNH2 or tBuNH2) both hydroamination isomeric imines Z and E were obtained. During the catalytic reaction, the E (kinetic) isomer is transformed into the most stable Z (thermodynamic) isomer. The unique reactivity of the alkyne (TMS) C identical to CH with the secondary amine Et2NH is remarkable because it afforded the trans dimer and the corresponding hydroamination enamine. The latter probably results from the insertion of the alkyne into a secondary metal-amide bond, followed by protonolysis.

Vibrational Photopolymerization of Methyl Methacrylate and Quantitative Analysis of Polymerization Results

Radical photopolymerization of methyl methacrylate (MMA) with 2,2‘-azobis(isobutyronitrile) (AIBN) as an initiator was carried out by visible light excitation. Excitation of the fifth vibrational overtone of the CH stretch of AIBN at 628 nm initiates the reaction with subsequent monomer conversion of up to 86% after 24 h. The quantitative analysis of monomer conversion was accomplished by a partial least-squares (PLS) analysis of the second vibrational overtone spectra of methyl, methylenic, and vinyl CH stretch absorptions. The wavelength selectivity of the process was studied by irradiating samples at the fifth vibrational overtone of the methyl CH stretch of AIBN (628 nm), the fifth vibrational overtone of vinyl CH stretch of MMA (602 nm), and a wavelength where both monomer and initiator do not absorb light (595 nm). The mixtures irradiated at the monomer absorption peak exhibited about 4 times less polymer formation than mixtures irradiated at the initiator absorption peak after 24 h. The overall quantum yields (φ) for 24 h of polymerization were estimated to be φ628 = 9937 and φ602 = 1810 for the mixtures irradiated at 628 and 602 nm, respectively.

Cyclovoltammetric studies on the reaction of dihydridotetrakis(triphenylphosphane)ruthenium(II) with methyl acrylate. CH-activation of methyl acrylate in the presence of Ru(0)(MA) 2(PPh 3) 2

Electrochemical studies on RuH 2(PPh 3) 4 ( 1) and Ru(0)(MA) 2(PPh 3) 2 ( 2), the complex that is generated when RuH 2(PPh 3) 4 is dissolved in methyl acrylate (MA), are carried out by cyclic voltammetry (CV). The combination of electrochemical with NMR spectroscopic measurements reveals that MA undergoes oxidative addition to Ru(0)(MA) 2(PPh 3) 2 via cleavage of a vinylic CH bond. The resulting hydridoruthenium(II) complex is not stable in MA and forms presumably a complex in which a further MA is inserted into the ruthenium–hydrogen bond.

Ether Complexes of Tungsten with Two Different Binding Modes: An O-Bound Ether and an η2-(CC) Vinyl Ether. Evidence for CH···O Hydrogen Bonding of Vinylic CH Groups

The reaction of PhCH(OCH3)2 with Cp(CO)3WH and HOTf gives [Cp(CO)3W(PhCH2OCH3)]+OTf-. The structure of this benzyl methyl ether complex was determined by single crystal X-ray diffraction and was shown to have the ether bonded to tungsten through the oxygen. This compound was isolated as a kinetic product of the reaction; it decomposes in solution by releasing free PhCH2OCH3 and forming Cp(CO)3WOTf. An analog with the BAr‘4- counterion [Ar‘ = 3,5-bis(trifluoromethyl)phenyl] is more stable. The reaction of the vinyl acetal CH2CHCH(OEt)2 with Cp(CO)3WH and HOTf produces [Cp(CO)3W(η2-EtOCHCHCH3)]+OTf-, in which the ether is bonded to tungsten through the CC bond of the vinyl ether. The crystal structure of this compound shows that the WC(OEt) distance (2.69(3) Å) is significantly longer than the WC(CH3) distance (2.37(3) Å). There are weak CH···O hydrogen bonds between both vinyl CH's and oxygens of triflate counterions. Evidence is presented that some of these weak hydrogen bonds are maintained in CD2Cl2 solution but not in CD3CN.

An infrared spectroscopic comparison of cis- and trans-CHCH and vinyl CHCH 2 group frequencies of some hexenes, heptenes, and stereospecific and non-stereospecific polybutadienes

The infrared bands of cis- and trans-CHCH and vinyl CHCH 2 groups of 1-hexene, trans-2-hexene, trans-3-hexene, 1-heptene, trans- and cis-2-heptene and cis-3-heptene are compared spectroscopically with the bands of the analogous chemical groups in six stereospecific and non-stereospecific polybutadienes with different cis-, trans- and vinyl microstructural composition. Special attention is given to the bands associated with the vibrations of the in-plane and out-of-plane CH deformation modes. The bands of the cis- and trans-CHCH groups appear at 1411-1405, 1310-1300, 1313-1310 and ≈ 1298 cm −1 for the cis ρ(CH)a, cis ρ(CH)s, trans ρ(CH)s and trans ρ(CH)a modes respectively of the olefins and polybutadienes. The trans ω(CH) mode appears at 975 cm −1 (with a band-width at half height of 16 cm −1) or 967 cm −1 (with a band-width of 21 cm −1) in the spectra of the olefins and the polybutadienes respectively. These values contrast sharply with those of the cis ω(CH) mode. The spectra of the olefins show that this mode absorbs infrared radiation at 713 cm −1 and has a band width at half height of 32 cm −1 for cis-2-heptene, or at 698 cm −1 with 44 cm −1 band-width for cis-3-heptene. The spectra of the polybutadienes show that the maximum absorption of this mode appears between 728 and 739 cm −1 with band-widths that vary between 70 and 40 cm −1. These observations indicate that the exact position and band-width of the cis ω(CH) is therefore very dependent on the configuration of the adjacent units, and possibly of units further removed. The bands of the vinyl group appear at 1422-1419, 1308-1295, 995 and 913 cm −1 for the δ(CH 2), ρ(CH), trans ω(CH)ip and ω(CH 2) modes of the olefins and polybutadienes. The cis ω(CH)ip mode splits into two bands at 632 cm −1 and 554 cm −1 in the spectra of the olefins; these bands are associated with the cis and skew rotational isomers of the olefins. Unfortunately these bands are not observed in the spectra of the polybutadienes because of the strong and broad absorption of the cis ω(CH) mode.