The insertion reaction mechanisms of siglet and striglet CCl2 with CH3CHO have been studied by using the DFT, NBO, CCSD(T) and AIM method. The geometries of reactions, transition state and products were completely optimized by B3LYP/6–31G(d). All the energy of the species was obtained at the CCSD(T)/6–31G(d,p) level. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only insert the Cα—H (reaction I) but also can react with Cβ—H (reaction II). There are three main existing pathways and the products are P1 (CH3COHCCl2), P2 (CH2COHCHCl2) and P4[CHCl2CHCHOH] respectively. Reaction II happens more easily according to the energy changes and the barrier in rate-controlling step. In addition, the important geometries in domain pathways have been studied by AIM theory. And also, the energy changes of H in the inserted C—H bond have been investigated.

Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde

The insertion reactions of CO2 with M—H(M=Co,Pd) and Pd—CH3 were systematically investigated by the first-principle DFT-GGA calculations.The mechanisms of CO2 reacting with M—H and Pd—CH3 were obtained for the direct synthesis of acetic acid from CH4/CO2 by a two-step reaction sequence on Co—Pd catalysts.The calculation result showed that the pathway that CO2 inserts into Co—H bonds forming HCOO—Co was the most advantageous in dynamics for all four designed reaction paths.However,HCOO was linked with Co in bi-dentate form,whose binding energy was very large,so the desorption of HCOO hardly taken place and formic acid was little produced.Meanwhile,the pathway that CO2 inserts into Pd—CH3 bonds forming H3CCOO—Pd was secondly preferential pathway favored in dynamics.The binding energy between H3CCOO and Pd was small,and desorption of H3CCOO easily occurred,so the main product was acetic acid.While methyl formate was inhibited by dynamics.The calculated result was in accordance with the experimental facts.

Density Functional Theory Study on Interaction of CO_2 with Metal Surface Carbon Species in Synthesis of Acetic Acid from CH_4/CO_2 on Co-Pd Catalysts

The structures of 5 7'-(iminomethyl)-bis-8-hydroxyquinoline(5 7'-iminomethylq(2)) and its metalorganic complexes M (5,7'-iminomethylq(2))(2) ( M = Zn, Mg, Be) were optimized at B3LYP/6-31G level. The absorption spectra based on the above structure were obtained by the time-dependent density functional theory TD-B3LYP with the 6-31G basis set. At the same time, dihydrogen bond in 5,7'-iminomethylq(2) and M (5,7'-iminomethylq(2))(2) were studied with NBO and AIM analysis. The calculated results of absorption spectrum for 5 7'-iminomethylq(2) has good agreement with the experimental data. All complexes are excellent electrontransporting materials, absorption spectrum wave bands of which can be tuned little by different metals on the ligand of 5,7'-(iminomethyl)-bis-8-hydroxyquinoline anion. The absorption of M(5 7'-iminomethylq(2))(2) have a substance red shift compared with that of 5 7'-iminomethylq(2). There are also hydrogen bonds in the molecules, which make the molecules more stable.

Theory Studies of 5,7 '-(Iminomethyl)-bis-8-hydroxyquinoline and Its Metal-Organic Complexes Via Dft, Nbo and Aim

The insertion and abstraction reaction mechanisms of singlet and triplet CCl2 with CH3MH (M=O, S) have been studied by using the DFT, NBO and AIM methods. The geometries of reactions, the transition state and products were completely optimized by B3LYP/6–311G(d, p). All the energy of the species was obtained at the CCSD(T)/6–311G(d, p) level. The calculated results indicated that the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CCl2 can not only trigger the insertion reaction with C-H and M-H in four pathways, by which the products P1 [CH3OCHCl2, reaction I(1)], P3[Cl2HCCH2OH, reaction I(2)], P5[CH3SCHCl2, reaction II(1)] and P7[Cl2HCCH2SH, reaction II(2)] are produced respectively, but also abstract M-H, resulting P4 [CH2O+CH2Cl2, reaction I(3)] and P8[CH2S+CH2Cl2, reaction II(3)]. In addition, the important geometries in domain pathways have been studied by AIM and NBO theories.

Quantum chemical study on insertion and abstraction reaction of dichlorocarbene with methyl alcohol and methyl mercaptan

The insertion reaction mechanism of CBr2 with CH3CHO has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD(T)/6-31G(d) level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that the propionaldehyde (HP1) is the main product of CH2 insertion with CH3CHO. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr2 not only can insert the Cα-H [reaction I(1)]) but also can react with Cβ-H [reaction II(1)]. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of I(1) and II(1) in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I(1) and II(1) respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I(1) more easily occurs, while the reactions are not selected in the temperature range of 1000–1600 K.

https://rd.springer.com/content/pdf/10.1007%2Fs11434-008-0056-4.pdf

Density functional theory calculation on the C-H bond insertion reaction of dibromocarbene with acetaldehyde

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Density functional theory calculation on the C-H bond insertion reaction of dibromocarbene with acetaldehyde

Quantum chemical and topological study on the insertion reaction of dichlorcarbene with acetaldehyde