Theoretical study of diels-alder reactions between substituted derivatives of butadiene and ethylene

The potential surfaces for the butadiene + ethylene and l-hydroxybutadiene+acrolein reactions, have been calculated (MINDO/2). A simplified study of the potential surface for several reactions between monosubstituted derivatives of butadiene and ethylene has also been done (MINDO/3). From the results obtained, the endo-exo ratio, the regioselectivity, the influence of substituents on the reaction rate and the mechanism of the process are discussed.     

Theoretical consideration of the role of the Franck—Condon factor in chemical reactions

A new cross section formula for stripping type chemical reactions is developed by making use of the Born approximation. The result indicates that Franck—Condon factors play an important role for the above type of chemical reaction.     

Theoretical investigation of the reaction of Mn+ with ethylene oxide

The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.     

Theoretical study of the gas-phase chemiionization reactions La + O and La + O2

The La + O and La + O 2 chemiionization reactions have been investigated with quantum chemical methods. For La + O 2(X (3)Sigma g) and La + O 2(a (1)Delta g), the chemiionization reaction La + O 2 --> LaO 2 (+) + e (-) has been shown to be endothermic and does not contribute to the experimental chemielectron spectra. For the La + O 2(X (3)Sigma g) reaction conditions, chemielectrons are produced by La + O 2 --> LaO + O, followed by La + O --> LaO (+) + e (-). This is supported by the same chemielectron band, arising from La + O --> LaO (+) + e (-), being observed from both the La + O( (3)P) and La + O 2(X (3)Sigma g) reaction conditions. For La + O 2(a (1)Delta g), a chemielectron band with higher electron kinetic energy than that obtained from La + O 2(X (3)Sigma g) is observed. This is attributed to production of O( (1)D) from the reaction La + O 2(a (1)Delta g) --> LaO + O( (1)D), followed by chemiionization via the reaction La + O( (1)D) --> LaO (+) + e (-). Potential energy curves are computed for a number of states of LaO, LaO* and LaO (+) to establish mechanisms for the observed La + O --> LaO (+) + e (-) chemiionization reactions.     

Theoretical approach to the mechanism of reactions between halogen atoms and unsaturated hydrocarbons: the Cl + propene reaction

The potential energy surface for the Cl + propene reaction was analyzed at the MP2 level using Pople's 6-31G(d,p) and 6-311+G(d,p), and Dunning's cc-pVDZ and aug-cc-pVDZ basis sets. Two different channels for the addition reaction leading to chloroalkyl radicals and five alternative channels for the abstraction reaction leading to C(3)H(5) (.) + HCl were explored. The corresponding energy profiles were computed at the QCISD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ level of theory. Theoretical results suggest that the previously established mechanism consisting of (1) direct abstraction and (2) addition-elimination steps is instead made up of (1) addition through an intermediate and (2) two-step abstraction processes. No direct abstraction mechanism exists on the potential energy surface. The kinetic equations derived for the new mechanism are consistent with the pressure dependence experimentally observed for this reaction.     

Theoretical survey of the gas-phase reactions of allylamine with Co+

Density functional theory calculations have been carried out to survey the gas-phase reactions of allylamine with Co+. The geometries and bonding characteristics of all the stationary points involved in the reactions have been investigated at the B3LYP/6-311++G(d,p) level. Final energies are obtained by means of the B3LYP/6-311+G(2df,2pd) single-point calculations. The performance of these theoretical methods is valuated with respect to the available thermochemical data. Co+ strongly binds allylamine by forming a chelated structure in which the metal cation binds concomitantly to the two functional groups of the neutral molecule. Various mechanisms leading to the loss of NH3, NH2, C2H2, and H2 are analyzed in terms of the topology of the potential energy surface. The most favorable mechanism corresponds to the loss of NH3, through a process of C-N activation followed by a concerted beta-H shift. The accompanying NH2 elimination is also discussed. The loss of C2H2 is also favorable, through C-C activation and stepwise beta-H shift, giving Co+(NH2CH3) and Co+H(NH2CH2) as the product ions. Various possible channels for the loss of H2 are considered. The most favorable mechanism of the H2 loss corresponds to a pathway through which the metal acts as a carrier, connecting a hydrogen atom from the methylidyne group of allylamine with a hydrogen atom of the terminal methylene group. The product ion of this pathway has a tricoordinated structure in which Co+ binds to the terminal two Cs and N atoms of the NH2CH2CCH moiety.     

An experimental and theoretical study of the reactions OIO+NO and OIO+OH

The kinetics of the reaction OIO+NO were studied by pulsed laser photolysis/time-resolved cavity ring-down spectroscopy, yielding k(235-320 K)=7.6(+4.0)(-3.1) x 10(-13) exp[(607+/-128)/T] cm3 molecule-1 s-1. Quantum calculations on the OIO+NO potential-energy surface show that the reactants form a weakly bound OIONO intermediate, which then dissociates to the products IO+NO2. Rice-Ramsberger-Kassel-Markus (RRKM) calculations on this surface are in good accord with the experimental result. The most stable potential product, IONO2, cannot form because of the significant rearrangement of OIONO that would be required. The reaction OIO+OH was then investigated by quantum calculations of the relevant stationary points on its potential-energy surface. The very stable HOIO2 molecule can form by direct recombination, but the bimolecular reaction channels to HO2+IO and HOI+O2 are closed because of significant energy barriers. RRKM calculations of the HOIO2 recombination rate coefficient yield krec,0=1.5x10(-27) (T/300 K)(-3.93) cm6 molecule-2 s-1, krec,infinity=5.5x10(-10) exp(46/T) cm3 molecule-1 s-1, and Fc=0.30. The rate coefficients of both reactions are fast enough around 290 K and 1 atm pressure for these reactions to play a potentially important role in the gas phase and aerosol chemistry in the marine boundary layer of the atmosphere.     

Theoretical elucidation of the rhodium-catalyzed [4 + 2] annulation reactions

The reaction mechanism of the Rh-catalyzed [4 + 2] annulation of 4-alkynals with isocyanates is unraveled using density functional calculations. The reaction mechanisms of the model system and the real substituted system have been investigated and the results are compared. From our theoretical results based on the model and real substituted system, it is shown that (a) the rate-determining step is the Rh-H addition to the alkyne, (b) the formation of the cyclopentenone G and glutarimide K represents a severe competition, and (c) the product selectivity should be controlled by the amount of the isocyanates. In addition, it is demonstrated that there exist steric effects in the real substituted system, but missed in model system. Our calculations also show that although the results obtained on the model system could explain the mechanism in principle, the real substituted system could reflect the mechanism more exactly and make the reaction proceed with regioselectivity.     

Hydrogenation reactions of ethylene on neutral vanadium sulfide clusters: experimental and theoretical studies

The reactions of C(2)H(4) with H(2) on neutral vanadium sulfide clusters in a fast flow reactor are investigated by time-of-flight mass spectrometry employing 118 nm (10.5 eV) single photon ionization. The experimental products of these reactions are V(m)S(n)C(2)H(x) (m=1, n=1-3; m=2, n=1-5, and x=4-6). Observation of these products indicates that these V(m)S(n) clusters have high catalytic activity for hydrogenation reactions of C(2)H(4). Density functional theory calculations at the BPW91/TZVP level are carried out to explore the geometric and electronic structures of the V(m)S(n) clusters and to determine reaction intermediates and transition states, as well as reaction mechanisms. All reactions are estimated as overall barrierless or with only a small barrier (0.1 eV), and are thermodynamically favorable processes at room temperature. The ethylene molecule is predicted to connect with active V atoms through its π-orbital or form a σ-bond with active V atoms of catalytic V(m)S(n) clusters. The S atoms bonding with active V atoms play an important role in the dissociation of the H(2) molecule; H atoms transfer to the C(2)H(4) (one after another) following breaking of the H-H bond. A catalytic cycle for C(2)H(4) hydrogenation reactions on a vanadium sulfide catalyst surface is suggested based on our experimental and theoretical investigations.     

Theoretical study on the mechanism of the 1CHCl + NO2 reactions

The radical-molecule reaction mechanism of (1)CHCl with NO(2) has been explored theoretically at the B3LYP/6-311G(d, p) and CCSD(T)/6-311G(d, p) (single-point) levels of theory. Thirteen minimum isomers and 29 transition states are located. The initial association between (1)CHCl and NO(2) proceeds most likely through the carbon-to-middle-nitrogen attack leading to an energy-rich adduct a (HClCNO(2)), which is found to be a barrierless process. Staring from a, the most feasible channel is to undergo a concerted O-shift and C--N bond rupture leading to product P(2) (NO + HClCO). The minor product pathways are the direct O-extrusion of a to P(3) (O + HClCNO-cis) as well as the 1,3-H-shift of a to isomer b (ClCNOOH) followed by a concerted OH-shift leading to d (HOClCNO), which will dissociate to product P(8) (NO + ClCOH) via C--N cleavage. Because the transition states and isomers involved in the most feasible channel all lie below the reactants, the title reaction is expected to be rapid, as is consistent with the measured rate constant at 296 K. The comparison with the analogous reactions (3)CH(2) + NO(2) are discussed. The present study may be useful for further experimental investigation of the title reaction.     

Gas-phase reactions of nitronium ions with acetylene and ethylene: an experimental and theoretical study

A comparative study of the gas-phase reactions of NO2+ with acetylene and ethylene was performed by using FT-ICR, MIKE, CAD, and NfR/ CA mass spectrometric techniques, in conjunction with ab initio calculations at the MP2/6-31+G* level of theory. Both reactions proceed according to the same mechanism, that is, 1,3-dipolar cycloaddition, but yield products of different stability. The C2H2NO2+ adduct from acetylene has an aromatic character and hence is highly stabilized with respect to the C2H4NO2+ adduct from ethylene. Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetaldehyde, which represent the thermodynamically most stable products from the addition of NO2+ to acetylene and ethylene, respectively. As prototypal examples of the reactivity of free nitronium ions with most simple pi systems, the reactions investigated are useful starting points to model the mechanism of aromatic nitration.     

Theoretical study on the mechanism of the cycloaddition reaction between stannylene and ethylene or formaldehyde

The mechanism of the cycloaddition reaction of singlet stannylene and ethylene or formaldehyde has been studied by using density functional theory. The geometrical parameters, harmonic vibrational frequencies and energies of stationary points for potential energy surface are calculated by RB3LYP/3–21G* method. The results show that the two reaction processes are both two steps: (1) stannylene and ethylene or formaldehyde form an energy‐rich intermediate complex respectively, which is an exothermal reaction with no barrier; (2) two intermediate complexes isomerize to the product, respectively, with the barriers of these two reactions being 52.97 and 45.15 kJ/mol at RB3LYP/3–21G* level.     

Theoretical study on the group 2 atoms + N2O reactions

The electronic structure aspects of the M (1S,3P) + N2O(X 1sigma+) (M = Be, Mg, Ca) reactions are investigated using the CASSCF/MRMP2 (complete active space SCF and the multireference M?ller-Plesset perturbation theory of the second order) computational methodology. The lowest adiabatic 1 1A' and 1 3A' potential energy surfaces (PESs) favor the bending dissociation mechanism of N2O in all studied cases. The rate-limiting channels are determined by the classical barriers that decrease in the series Be (8.9) > Mg (7.0) > Ca (1.2) kcal/mol, whereas the spin-forbidden reaction channels are found to be less important. A comparison with elaborated kinetic results (Plane et al. J. Phys. Chem. 1990, 94, 5255; Gas-Phase Metal Reactions; Elsevier: Amsterdam, 1992; Vinckier et al. J. Phys. Chem. A 1999, 103, 5328) on the Ca (1S) + N2O(X 1sigma+) reaction is presented, and the differences in the kinetic behavior of the title reactions are discussed. Our results also indicate that the techniques based on the multiconfigurational wave functions are unavoidable if a correct topology of the PESs governing these reactions is needed.     

Theoretical studies on cycloaddition reactions between keteniminium cations and olefins

The mechanisms of seven reactions between keteniminium cations and olefins have been theoretically explored at BHandHLYP/6-31G level. It is found that these seven reactions always form a relatively stable hydrogen-bonded type of ion-molecule complex first except for reactions 1d+2a and 1e+2a, which have no hydrogen atom attached to nitrogen atom in keteniminium cations. Some reactions take place via a concerted but unsynchronous mechanism, and the others are stepwise processes. The substituent effects are also studied. The data reveal that the electron-pushing substituents on keteniminium cations disfavor the reaction, and the electron-attracting substituents on keteniminium cations favor the reactions. The substituent effects on ethene are contrary to the former case.     

Density functional study of Diels-Alder reactions between cyclopentadiene and substituted derivatives of ethylene

Diels-Alder reactions of cyclopentadiene with ethylene, acrylonitrile, and acrolein were theoretically studied using density functional methods. The results obtained were compared with those corresponding to ab initio methods. Density functional methods, using the B-LYP nonlocal functional, or hybrid methods, yield energy barriers in excellent agreement with the experimental data. For the reactions with substituted derivatives of ethylene, the results show that acrylonitrile reacts with cyclopentadiene with virtually no stereoselectivity, while for acrolein, the formation of the endo product is predicted to be the most favorable from the values of activation Gibbs energies. © 1997 John Wiley & Sons, Inc.     

2-硅萘与2,3-二甲基丁二烯的杂Diels-Alder反应的理论研究

采用密度泛函B3LYP/6-311G**方法研究了2-硅萘作为亲二烯体与2,3-二甲基丁二烯的杂Diels-Alder反应的微观机理、势能剖面、取代基效应及溶剂效应,并与硅苯参与的类似反应进行了比较.计算结果表明,所研究反应均以协同非同步的方式进行,且C-Si键总是先于C-C键形成.发生在C1-Si2位上的反应中两个新...     

Theoretical and experimental investigations on the reactions of positively charged phenyl radicals with aromatic amino acids

The chemical behavior of positively charged phenyl radicals 3-dehydro-N-phenylpyridinium (a), N-(3-dehydro-5-chlorophenyl)pyridinium (b), and N-(3-dehydrophenyl)pyridinium (c) toward L-tyrosine, phenylalanine, and tryptophan was investigated in the gas phase both theoretically by performing molecular orbital calculations and experimentally by using FT/ICR mass spectrometry. All radicals react with phenylalanine and tryptophan nearly at the collision rate. The overall reactivity of the radicals toward tyrosine follows the order a > b > c, which is consistent with the electron affinity (EA) ordering of the radicals. The higher the electrophilicity (or EA) of the radical, the greater the reactivity. As expected, all radicals abstract a hydrogen atom from all of the amino acids. However, the most electrophilic radical a was also found to react with these amino acids via NH2 abstraction. A new reaction observed between radicals a-c and aromatic amino acids is the addition of the radical to the aromatic ring of the amino acid followed by Calpha-Cbeta bond cleavage, which leads to side-chain abstraction by the radical.     

Theoretical study of the F + NH3 and F + ND3 reactions: mechanism and comparison with experiment

We study the barrierless and highly exothermic F + NH(3) and F + ND(3) abstraction reactions using quasiclassical trajectory calculations based on an analytical potential energy surface developed in our research group. The calculations correctly reproduce the experimental evidence that the vibrational fraction deposited into the DF product for the F + ND(3) reaction is greater than into HF for the F + NH(3) reaction and that the vibrational distribution is inverted in the HF(v') and the DF(v') products. Of special interest is that recent crossed-beam experiments reported by Yang and co-workers at 4.5 kcal mol(-1) are reproduced for both reactions, with a mainly forward symmetry associated with direct trajectories, and a small sideways-backward symmetry contribution associated with "nearly trapped" trajectories due to a "yo-yo" mechanism, different from the previously suggested mechanism of a long-lived complex.