Reactions of Criegee Intermediates are Enhanced by Hydrogen-Atom Relay Through Molecular Design

We report a type of highly efficient double hydrogen atom transfer (DHAT) reaction. The reactivities of 3-aminopropanol and 2-aminoethanol towards Criegee intermediates (syn- and anti-CH₃CHOO) were found to be much higher than those of n-propanol and propylamine. Quantum chemistry calculation has confirmed that the main mechanism of these very rapid reactions is DHAT, in which the nucleophilic attack of the NH₂ group is catalyzed by the OH group which acts as a bridge of HAT. Typical gas-phase DHAT reactions are termolecular reactions involving two hydrogen bonding molecules; these reactions are typically slow due to the substantial entropy reduction of bringing three molecules together. Putting the reactive and catalytic groups in one molecule circumvents the problem of entropy reduction and allows us to observe the DHAT reactions even at low reactant concentrations. This idea can be applied to improve theoretical predictions for atmospherically relevant DHAT reactions.     

Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH₂OO and CH₃CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH₃COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity‐enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10^?10 cm³ s^?1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.     

Temperature‐Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates

The rate coefficients for gas‐phase reaction of trifluoroacetic acid (TFA) with two Criegee intermediates, formaldehyde oxide and acetone oxide, decrease with increasing temperature in the range 240–340 K. The rate coefficients k(CH₂OO + CF₃COOH)=(3.4±0.3)×10⁻¹⁰ cm³ s⁻¹ and k((CH₃)₂COO + CF₃COOH)=(6.1±0.2)×10⁻¹⁰ cm³ s⁻¹ at 294 K exceed estimates for collision‐limited values, suggesting rate enhancement by capture mechanisms because of the large permanent dipole moments of the two reactants. The observed temperature dependence is attributed to competitive stabilization of a pre‐reactive complex. Fits to a model incorporating this complex formation give k [cm³ s⁻¹]=(3.8±2.6)×10⁻¹⁸ T² exp((1620±180)/T) + 2.5×10⁻¹⁰ and k [cm³ s⁻¹]=(4.9±4.1)×10⁻¹⁸ T² exp((1620±230)/T) + 5.2×10⁻¹⁰ for the CH₂OO + CF₃COOH and (CH₃)₂COO + CF₃COOH reactions, respectively. The consequences are explored for removal of TFA from the atmosphere by reaction with biogenic Criegee intermediates.     

The Origin of the Reactivity of the Criegee Intermediate: Implications for Atmospheric Particle Growth

The electronic structure of the simplest Criegee intermediate, H₂COO, is practically that of a closed shell. On the biradical scale (β), where 0 corresponds to the pure closed shell and 1 to a pure biradical, its β value is only 0.10, suggesting that its ground electronic state is best described as a H₂C=O^δ+?O^δ? zwitterion. However, this picture of a nearly inert closed shell contradicts its rich reactivity in the atmosphere. It is shown that the mixing of its ground state with the first triplet excited state, which is a pure biradical state of the type H₂C^.?O?O^., is responsible for the formation of strongly bound products during reactions inducing atmospheric particle growth.     

Functionalized Hydroperoxide Formation from the Reaction of Methacrolein-Oxide,an Isoprene-Derived Criegee Intermediate,with Formic Acid: Experiment and Theory

Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at m/z 99, consistent with the proposed mechanism and characteristic loss of HO₂ upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis.     

Criegee中间体CH_3CHOO与OH自由基反应机理的理论研究

采用CCSD(T)//B3LYP/6-311+G(d,p)方法研究了Criegee中间体CH_3CHOO与OH自由基反应的微观机理.结果表明,上述反应存在抽氢、加成-分解和氧化3类反应通道,其中,syn-CH3CHOO+OH以抽β-H为优势通道,表观活化能为-4.88 k J/mol;anti-CH_3CHOO+OH则以加成-分解反应为优势通道,表观活化能为-13.25 k J/mol.在加成-分解和氧化反应通道中,anti-构象的能垒均低于syn-构象,而抽氢反应则是syn-(β-H)的能垒低于anti-构象.速率常数计算表明,anti-构象的加成-分解反应通道具有显著的负温度效应;syn-和anti-构象的氧化通道具有显著的正温度效应.3类反应具有显著不同的温度效应,说明通过改变温度可显著调节3类反应的相对速率.     

Criegee中间体气相反应热力学的G2理论计算

Criegee intermediate is believed to play an important role in the atmospheric chemistry. Because of its short life and the difficulty in experimental study, we carried out ah initio calculations on the thermochemistry of the Criegee involving reactions in this study. Thermochemistry data of reaction enthalpies and Gibbs free energies for four different stable structures of the Criegee intermediates (singlet CH2OO ①1 A1 in C2v, triplet CH2OO ②3B1 in C2v, singlet CH2OO ③1A' in Cs and triplet CH2OO ④ in C1 symmetry) involved in some of the gas-phase reactions were calculated at the standard Gaussian-2 [G2(MP2) and G2] and a modified G2, G2(fu1)[10],levels of theory. Relative energies among those Criegees and formic acid were compared. Chemical reactions include the formation of Criegees, re-arrangement from Criegee to formic acid, dissociations (producing CH2(3B1)+O2, CH2(1A1)+O2, CO2+H2, CO2+2H, CO+H2O, OH+HCO) and the reactions between Criegee and NO/H2O. Standard equilibrium constants for some reactions were investigated and may be obtained for all of the rest reactions involved in this study by the standard Gibbs free energies. It is shown that the formation of Criegee ①-④ by ethylene and ozone, the re-arrangement from any Criegee to formic acid, the dissociation in producing CO2+O2and CO+H2O and the reactions between any Criegee and NO/H2O are all favourable thermodynamicaly. The dissociation in forming CO2+2H and OH+HCO is less favourable. While the dissociation in forming carbene (either in 3B1 or 1A1 state) is not allowed by ΔrGm? values. Standard enthalpies of formation at 298 K for the four Criegees were predicted at the G2(ful) level of theory. Each value is the average value from ten of the above reactions and they are -4.3, 74.8,98.9 and 244.6 kJ mol-1 at the G2(ful) level for Criegee ① to Criegee ④, respectively. In addition, tile standard enthalpy of formation at 298 K for HOCH2OOH is further predicted to be -315.6 kJ mol-1 at the G2(MP2) level.     

Infrared Detection of Criegee Intermediates Formed during the Ozonolysis of β‐Pinene and Their Reactivity towards Sulfur Dioxide

Recently, direct kinetic experiments have shown that the oxidation of sulfur dioxide to sulfur trioxide by reaction with stabilized Criegee intermediates (CIs) is an important source of sulfuric acid in the atmosphere. So far, only small CIs, generated in photolysis experiments, have been directly detected. Herein, it is shown that large, stabilized CIs can be detected in the gas phase by FTIR spectroscopy during the ozonolysis of β‐pinene. Their transient absorption bands between 930 and 830 cm^?1 appear only in the initial phase of the ozonolysis reaction when the scavenging of stabilized CIs by the reaction products is slow. The large CIs react with sulfur dioxide to give sulfur trioxide and nopinone with a yield exceeding 80 %. Reactant consumption and product formation in time‐resolved β‐pinene ozonolysis experiments in the presence of sulfur dioxide have been kinetically modeled. The results suggest a fast reaction of sulfur dioxide with CIs arising from β‐pinene ozonolysis.     

N-Heterocyclic Carbenes as Key Intermediates in the Synthesis of Fused,Mesoionic, Tricyclic Heterocycles

Coupling between 5-bromoimidazo[1,5-a]pyridinium salts and malonate or arylacetate esters leads to a facile and straightforward access to the new mesoionic, fused, tricyclic system of imidazo[2,1,5-cd]indolizinium-3-olate. Mechanistic studies show that the reaction pathway consists of nucleophilic aromatic substitution on the cationic, bicyclic heterocycle by an enolate-type moiety and in the nucleophilic attack of a transient free N-heterocyclic carbene (NHC) species on the ester group; the relative order of these two steps depends on the nature of the starting ester. This work highlights the valuable implementation of free NHC species as key intermediates in synthetic chemistry, beyond their classical use as stabilizing ligands or organocatalysts.     

Temperature-dependent kinetics of the simplest Criegee intermediate reaction with dimethyl sulfoxide

Criegee intermediates are thought to play roles in atmospheric chemistry, including OH radical formation, oxidation of SO₂, NO₂, etc. CH₂OO is the simplest Criegee intermediate, of which the reactivity has been a hot topic. Here we investigated the kinetics of CH₂OO reaction with dimethyl sulfoxide (DMSO) under 278–349 K and 10–150 Torr. DMSO is an important species formed in the oxidation of dimethyl sulfide in the biogenic sulfur cycle. The concentration of CH₂OO was monitored in real-time via its mid-infrared absorption band at about 1,286 cm⁻¹ (Q branch of the ν₄ band) with a high-resolution quantum cascade laser spectrometer. The 298 K bimolecular rate coefficient was determined to be k₂₉₈ = (2.3 ± 0.3) × 10⁻¹² cm³/s at 30 Torr with an Arrhenius activation energy of −3.9 ± 0.2 kcal/mol and a weak pressure dependence for pressures higher than 30 Torr (k₂₉₈ = (2.8 ± 0.3) × 10⁻¹² cm³/s at 100 Torr). The reaction is speculated to undergo a five-membered ring intermediate, analogous to that of CH₂OO with SO₂. The negative activation energy indicates that the rate-determining transition state is submerged. The magnitude of the reaction rate coefficient lies in between those of CH₂OO reactions with (CH₃)₂CO and with SO₂.     

Criegee中间体RCHOO(R=H,CH_3)与NCO的反应机理

采用CCSD(T)/aug-cc-p VTZ//B3LYP/6-311+G(2df,2p)方法对Criegee中间体RCHOO(R=H,CH_3)与NCO反应的机理进行了研究,利用经典过渡态理论(TST)并结合Eckart校正模型计算了标题反应在298~500 K范围内优势通道的速率常数.结果表明,上述反应包含亲核加成、氧化和抽氢3类机理,其中每类又包括NCO中N和O分别进攻的两种形式.亲核加成反应中O端进攻为优势通道,氧化和抽氢反应则是N端进攻为优势通道;甲基取代使CH_3CHOO反应活性高于CH2OO;anti-CH_3CHOO的加成及氧化反应活性高于syn-CH_3CHOO,而抽氢反应则是syn-CH_3CHOO的活性高于anti-CH_3CHOO.anti-构象对总速率常数的贡献大于syn-构象,且总速率常数具有显著的负温度效应.     

An Intramolecular Hydrogen-Shift in a Peroxy Radical at Cryogenic Temperatures: The Reaction of 2-Hydroxyphenyl Radical with O2

Peroxy radical hydrogen-shifts are pivotal elementary reaction steps in the oxidation of small hydrocarbons in autoignition and the lower atmosphere. Although these reactions are typically associated with a substantial barrier, we demonstrate that the [1,5]H-shift in the peroxy species derived from the 2-hydroxyphenyl radical 1 is so facile that it even proceeds rapidly in an argon matrix at 35 K through a proton-coupled electron transfer mechanism. Hydrogen-bound complexes of o-benzoquinone are identified as the main reaction products by infrared spectroscopy although their formation through O−O bond scission is hampered by a barrier of 11.9 kcal mol⁻¹ at the ROCCSD(T)/cc-pVTZ/UB3LYP/6–311G(d,p) level of theory.     

Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3: Kinetics and Atmospheric Implications

Criegee intermediates (CIs) are a class of reactive radicals that are thought to play a key role in atmospheric chemistry through reactions with trace species that can lead to aerosol particle formation. Recent work has suggested that water vapor is likely to be the dominant sink for some CIs, although reactions with trace species that are sufficiently rapid can be locally competitive. Herein, we use broadband transient absorption spectroscopy to measure rate constants for the reactions of the simplest CI, CH₂OO, with two inorganic acids, HCl and HNO₃, both of which are present in polluted urban atmospheres. Both reactions are fast; at 295 K, the reactions of CH₂OO with HCl and HNO₃ have rate constants of 4.6×10^?11 cm³ s^?1 and 5.4×10^?10 cm³ s^?1, respectively. Complementary quantum‐chemical calculations show that these reactions form substituted hydroperoxides with no energy barrier. The results suggest that reactions of CIs with HNO₃ in particular are likely to be competitive with those with water vapor in polluted urban areas under conditions of modest relative humidity.     

Criegee中间体CH3CHOO与H2O反应机理及酸催化效应

采用CCSD（T）//B3LYP/6-311+G（d,p）方法研究了H₂O及甲酸等6种有机酸对CH₃CHOO与H₂O加成反应的催化作用。结果表明,非催化反应存在双质子迁移和加成反应2条通道,其中加成反应为优势通道。其加成机理为H₂O中OH加到CH₃CHOO的α-C上,同时H₂O中另一个H迁移到CH₃CHOO的端O上。催化剂H₂O及有机酸以氢键复合物的形式参与反应促进了H质子转移,可降低基元反应能垒和表观活化能,且催化效应与有机酸的强度成正比。例如,当分别用H₂O（pK_a=15.7）、甲酸（pK_a=3.75）和草酸（pK_a=1.23）催化时,生成syn-HAHP的基元反应能垒由非催化的69.12 kJ·mol^-1分别降至40.78、18.88和10.61 kJ·mol^-1。非催化反应具有正的表观活化能,而所有催化反应则均具有负的表观活化能。     

Promotion of Trimethylsilylation of Phenols by Trifluoroacetic Acid

Abstract

The speed of trimethylsilylation of sterically hindered phenols was increased by promoting the reaction with a small amount of trifluoroacetic acid. Promotion was successful with hexamethyldisilazane, trimethylchlorosilane, bis-(trimethylsilyl)-trifluoroacetamide, bis-(trimethylsilyl)-acetamide, and trimethylsilylimidazole.     

Thiocyanation of Allylic Alcohols Promoted by Trifluoroacetic Acid

A rapid and efficient acid-promoted strategy to access allylic thiocyanates using allylic alcohols as substrates and easily-available NH₄SCN as the thiocyanate source is presented under metal- and oxidant-free conditions. Through screening of various kinds of acids, organic and strong trifluoroacetic acid (TFA) was found most effective. Testing of substrates showed that the strategy has remarkable functional group tolerance. A possible mechanism is provided, and the gram-scale experiment demonstrate that this novel protocol has potential industrial application value.     

Identification of the D(3h) isomer of carbon trioxide (CO3) and its implications for atmospheric chemistry.

The CO3 molecule is considered an important reaction intermediate in the atmospheres of Earth and Mars for quenching electronically excited oxygen atoms and in contributing to the anomalous 18O isotope enrichment. The geometry of the CO3 intermediate plays an important role in explaining these effects; however, only the cyclic (C(2v)) isomer has been experimentally confirmed so far. Here, we report on the first spectroscopic detection of the acyclic (D(3h)) isomer of carbon trioxide (12C16O3) via its nu1 and nu2 vibrational modes centered around 1165 cm(-1) under matrix isolation conditions; the identification of the 12C18O3, 13C16O3, 13C18O3, 16O12C18O2, and 18O12C16O2 isotopomers of the acyclic isomer confirms the assignments.     

Ro-vibrational Spectra of the Simplest Deuterated Criegee Intermediate CD2OO

Criegee intermediates are of significance in the atmospheric chemistry. In this work, the ro-vibrational spectra of the simplest deuterated Criegee intermediate, CD\begin{document}$ _2 $\end{document}OO, were studied by a vibrational self-consistent field/virtual configuration interaction (VSCF/VCI) method based on a nine-dimensional accurate potential energy surface and dipole surface for its ground electronic state. The calculated fundamental vibrational frequencies and rotational constants are in excellent agreement with the available experimental results. These data are useful for further spectroscopic studies of CD\begin{document}$ _2 $\end{document}OO. Especially, the rotational constants for excited vibrational levels are essential for experimental spectral assignments. However, the infrared intensities from different resources, including the current computation, the experiment, and previous calculations at the NEVPT2 and B3LYP levels, deviate significantly.