Theoretical study of reactions between MH (M=B, Al) and the H<sub>2</sub>S molecule

Chen, Xian-Yang; Zhao, Chongchong; Yin, Ping; Gao, Ju

doi:10.1002/qua.1180

Cited by 8 publications

(6 citation statements)

References 25 publications

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“…Furthermore, carbene insertion with C-H of ether has been studied systemically by Lin et al [12][13][14][15] . Methods of calculating quantum chemistry are effective tool to study the mechanisms of reactions [10][11][12] and further, the characters of thermodynamics and kinetics have been studied deeply by using the theory of statistical thermodynamics and Eyring transition state theory with Wigner correction and some interesting results have been obtained [16][17][18] . The simple aldehyde is a good target in carbene and C-H insertion reaction and also acetaldehyde insertion reaction with C-H has been reported [19] .…”

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confidence: 99%

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

Yang

et al. 2008

Chin. Sci. Bull.

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The insertion reaction mechanism of CBr 2 with CH 3 CHO 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 ( H P1) is the main product of CH 2 insertion with CH 3 CHO. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr 2 not only can insert the C α -H [reaction I(1)]) but also can react with C β -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.

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confidence: 99%

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

Yang

et al. 2008

Chin. Sci. Bull.

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“…In addition, the structure parameters of main path in MP2/6-311G(d) are consistent with the B3LYP/ 6-311G(d), while the energy in G2MP2 is in accord with CCSD(T)/6-311G(d), further confirming that the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) are reliable in reactions. Recently, the theory of statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the reactions thermodynamic and kinetic characters [13,[20][21][22] , and some interesting results have been obtained. In this paper, according to statistical thermodynamics method and theoretics of Erying transition state corrected with Wigner, the variation of thermodynamical function and reaction rate constant k(T) have been calculated with our own programs.…”

Section: Calculation Methodsmentioning

confidence: 99%

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

Kang

et al. 2007

CHINESE SCI BULL

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The insertion reaction mechanism of CBr 2 with CH 3 CH 2 O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions, transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path, which proceeds via two steps: i) two reactants form an intermediate (IM1), which is an exothermal reaction of 8.62 kJ·mol −1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift, in which the energy barrier is 44.53 kJ·mol −1 . The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm, in which the reaction has a bigger spontaneity capability, equilibrium constant (K) and higher rate constant (k).dibromocarbene, formaldehyde, insertion reaction, density functional theory, thermodynamic and kinetic characters Carbene has been paid more attention to because it has some advantages, such as significant role in medicament synthesization and tensile annulet, and can speed up the reaction and make the reaction readily [1][2][3] . Herein, the reactions of carbene with mulriple bond, such as , and have been reported systemically [4][5][6] . Also, the addition reactions between dihalocarbenes and carbonyl compounds have been studied more and more deeply [7][8][9] . Methods of calculating quantum chemistry are effective tool to study the mechanisms of reactions [10][11][12] and further, the cycloaddition reactions of carbene with formaldehyde have been studied deeply by using calculating methods of quantum [13,14] . The insertion reactions between carbene and organic compounds also are reported [15,16] . Recently, the insertion reactions of carbene with ethers have been studied systemically [17][18][19] . However, to our knowledge, up to the present, there have been few literatures on the study of the insertion reactions between the carbene and formaldehyde. In the present work, both the insertion reaction mechanism between singlet CBr 2 and CH 2 O and the characters of thermodynamics and kinetics have been studied by using density functional theory (DFT) in B3LYP/6-311G(d) level. Moreover, our study can make up for the shortage of the study on insertion reaction between CBr 2 and CH 2 O in theories and experiments. Calculation methodsB3LYP/6-311G(d) implemented in the Gaussian 2003 package were employed to locate all the stationary points along the reaction pathways. Full optimization and vibrational analysis were done for the stationary points on the reaction profile. Zero-point energy and

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“…In the first step, the single bonds of N(6)AH (7) and N(14)ACl(15) break, two single-bonds N(6)AN (14) and H(7)ACl(15) form simultaneously. The bond lengths of the N(6)AH (7), N(14)ACl (15), N(6)AN (14), and H (7)ACl (15) change from 1.011, 2.004, 1.815, and 1.502 Å to 1.331, 3.000, 1.347, and 1.287 Å , respectively. In the second step, H(8) atom transfers from N(6) to .…”

Section: Geometriesmentioning

confidence: 96%

“…In the third step, the bond lengths of H(7)ACl (15) and O(13)AN (14) increase, and H(7) atom combine with O(13) atom to produce water. The bond lengths of the H(7)ACl(15), O(13)A N (14), N(6)ACl (15), and H(7)AO(13) change from 1.287, 1.363, 3.057, and 1.115 Å to 1.675, 1.896, 2.194, and 0.965 Å , respectively. In the fourth step, Cl(15) atom transfers from N(6) to C(3) and C(3)AN(6) bond length increases simultaneously.…”

Section: Geometriesmentioning

confidence: 98%

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A density functional theory study on diazotization and nitration of 3,5‐diamino‐1,2,4‐triazole

Lian¹,

Lai²,

Wang³

et al. 2011

Int J of Quantum Chemistry

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ABSTRACT:The reaction mechanism, thermodynamic and kinetic properties for diazotization and nitration of 3,5-diamino-1,2,4-triazole were studied by a density functional theory. The geometries of the reactants, transition states, and intermediates were optimized at the B3LYP/6-31G (d, p) level. Vibrational analysis was carried out to confirm the transition state structures, and the intrinsic reaction coordinate (IRC) method was used to explore the minimum energy path. The single-point energies of all stagnation points were further calculated at the B3LYP (MP2)/6-311þG (2d, p) level. The statistical thermodynamic method and Eyring transition state theory with Wigner correction were used to study the thermodynamic and kinetic characters of all reactions within 0-25 C. Two reaction channels are computed, including the diazotization and nitration of 3-NH 2 or 5-NH 2 , and there are six steps in each channel. The reaction rate in each step is increased with temperature. The last step in each channel is the slowest step. The first, second, and fifth steps are exothermic reactions, and are favored at lower temperature in the thermodynamics.

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Theoretical study of reactions between MH (M=B, Al) and the H₂S molecule

Cited by 8 publications

References 25 publications

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

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

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

A density functional theory study on diazotization and nitration of 3,5‐diamino‐1,2,4‐triazole

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Theoretical study of reactions between MH (M=B, Al) and the H2S molecule

Cited by 8 publications

References 25 publications

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

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

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

A density functional theory study on diazotization and nitration of 3,5‐diamino‐1,2,4‐triazole

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Theoretical study of reactions between MH (M=B, Al) and the H₂S molecule