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Volume # 2(135), March - April 2021 — "Calculation of interaction mechanism for complex catalyst HF-BF3 with p-methylstyrene in toluene with stoichiometric composition 1:1:1 by AB INITIO method"
Back to volume # 2(135) , March - April 2021
Received: February 2021

DOI 10.17677/fn20714807.2021.02.02

Fluorine Notes, 2021, 135, 3-4

Calculation of interaction mechanism for complex catalyst HF-BF3 with p-methylstyrene in toluene with stoichiometric composition 1:1:1 by AB INITIO method

V.A. Babkin1, D.S. Andreev1, A.V. Ignatov1, V.S. Belousov2, E.S. Titova3.4, A.I. Rakhimov3, V.T. Fomichev5

1 Volgograd State Technical University (Sebryakovsky br.), 403343 Volgograd Region, Mikhailovka, Michurin st., 21,
e-mail: babkin_v.a@mail.ru
2 I.M. Sechenov 1st Moscow State Medical University, 119991, Trubetskaya st., 8, bld. 2,
e-mail: desdemosha@mail.ru
3 Volgograd State Technical University, 400005, Volgograd, Lenin av., 28,
e-mail: organic@vstu.ru
4 Volgograd State Medical University, 400131, Pavshikh Bortsov sq., 1,
e-mail: titova051@rambler.ru
5 Architecture and Construction Institute (Volgograd State Technical University),
400074, Volgograd, Academic st. 1

Abstract: For the first time, a quantum-chemical study of initiation mechanism for monomer of п-methylstyrene cationic polymerization in the presence of a complex catalyst boron fluoride-hydrogen fluoride in toluene (with stoichiometric composition 1:1:1) was carried out by ab initio method. It was shown that activation energy of this reaction is 76 kJ/mol, and the thermal effect is 0 kJ/mol.

Keywords: p-methylstyrene, initiation mechanism, catalyst boron fluoride-hydrogen fluoride, toluene, reaction heat, ab initio method.

Introduction

Until now, a number of important fundamental questions remains unstudied, in particular, the questions, concerning the mechanisms of elementary acts of n-methylstyrene cationic polymerization, i.e initiation, growth and chain termination in the presence of a complex catalyst BF3 ∙ HF in toluene. Therefore, the aim of this paper is to study the mechanism of n-methylstyrene initiation (within the framework of molecular model) in the presence of said complex catalyst by calculation of interaction reaction between monomer and initiator along the RC1-H20 coordinate in toluene (with stoichiometric composition 1:1:1).

Methodical part

The initiation mechanism of monomer cationic polymerization for n-methylstyrene in the presence of a complex catalyst BF3 ∙ HF in toluene (with a stoichiometric mixture of 1:1:1) was studied. The distance between C(1) and H(20) atoms was chosen as a reaction coordinate. The calculation was carried out by ab initio RHF/6-311G** quantum chemical method [1] with geometry optimization for all parameters by gradient method incorporated into Firefly program [2] and based on GAMESS source code [1, 3]. This method was chosen due to the fact that it allows one to accurately calculate the energy barriers of a reaction and determine the active centers [3]. The calculations were performed within the framework of isolated molecule in toluene. The initiation mechanism of n-methylstyrene was realized according to the procedure described in detail in [4] and applied in papers [5-8]. The MacMolPlt program was used to visualize of molecule [9].

Calculation data

The calculation data for changes in bond lengths along the path of interaction, bond angles, atomic charges within molecular system during interaction of n-methylstyrene with BF3 ∙ HF catalyst in toluene (with stoichiometric composition 1:1:1) are presented in Table 1-3.

In Fig. 1 shows the geometric and electronic structure of initial model of n-methylstyrene, in Fig. 2 - the final structure of interaction of catalyst with p-methylstyrene, in Fig. 3 - the energy profile of this interaction, and in Fig. 4 – the change in atomic charges that directly involved in the interaction of complex catalyst HF·BF3 with p-methylstyrene.

Atoms C(1), C(2), H(20), F(21) and B(22) are directly involved in initiation of polymerization. Let us analyze the change in these atomic charges along selected reaction coordinate.

At the coordination stage (Stage 1, Steps 1-7), the atomic charge on C(1) changes from - 0.209 to - 0.245, at the stage of active center (AC) formation (Stage 2, Steps 8-17) - from - 0.257 to - 0.351, at the stage of final product formation (Stage 3, Steps 18-21) - from - 0.369 to - 0.245.

At the 1st stage, the atomic charge on C(2) changes from - 0.174 to - 0.178, at the 2nd stage - from - 0.173 to - 0.075, at the 3rd stage - from - 0.022 to - 0.110.

At the coordination stage, the atomic charge on H(20) changes from - 0.325 to - 0.329, at the AC formation stage - from - 0.366 to - 0.407, at the stage of final product formation - from 0.416 to 0.195.

At the 1st stage, the atomic charge on F(21) changes from - 0.334 to - 0.351, at the 2nd stage - from - 0.356 to - 0.440, at the 3rd stage - from - 0.441 to - 0.472.

At the coordination stage, the atomic charge on B(22) changes from - 0.816 to - 0.821, at the AC formation stage - from - 0.823 to - 0.847, and at the stage of final product formation - from 0.860 to 0.866.

The toluene atomic charges on (C(26)-C(32) and H(33)-H(40)) along the reaction coordinate varied in the following ranges: for C(26)-C(32) - from -0.175 to - 0.172 , for H(33)-H(40) - from 0.118 to 0.148. During this reaction, the F(21)-H(20) bonds are broken simultaneously, and the C(1)-C(2) double π-bond is transformed into a single σ-bond, a new bond C(1)-H(20) and a counter-ion [BF3 ∙ OH]– (Fig. 2).

Calculated value of reaction activation energy was 76 kJ/mol, and the value of thermal effect was 0 kJ/mol.

Thus, the change in atomic charges, the behavior of reaction fragments, the breaking of old bonds and formation of new bonds in reaction studied indicate that it proceeds according to coordinated interactions scheme.

Figure 1. The structure of initial model for complex catalyst HF·BF3 with p-methylstyrene in toluene (the stoichiometric composition 1:1:1)

Figure 2. The final interaction structure of complex catalyst H2O·BF3 with p-methylstyrene in toluene (the stoichiometric composition 1:1:1)

Figure 3. Change in total energy (E, kJ/mol) in the interaction process of the complex catalyst H2O·BF3 with p-methylstyrene in toluene (the stoichiometric composition 1:1:1)

Figure 4. Change in atomic charges (Q) on C(1), C(2), H(20) and F(21) atoms along the coordinate of reaction studied (1-21 - № of step).

Table 1. Change in bond lengths along the interaction pathway of complex catalyst HF-BF3 with p-methylstyrene in toluene (the stoichiometric composition of 1:1:1)

No of step

1

2

3

4

5

6

7

8

9

10

C(2)-C(1)

1,32

1,32

1,33

1,33

1,33

1,33

1,33

1,33

1,33

1,33

H(3)-C(2)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(4)-C(1)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(5)-C(1)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

C(6)-C(11)

1,39

1,39

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

C(6)-C(2)

1,48

1,48

1,48

1,48

1,48

1,48

1,48

1,48

1,48

1,48

C(7)-C(6)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(8)-C(7)

1,38

1,38

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(9)-C(8)

1,39

1,39

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

C(10)-C(9)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(11)-C(10)

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

H(12)-C(7)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(13)-C(8)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(14)-C(10)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(15)-C(11)

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

C(16)-C(9)

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

H(17)-C(16)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(18)-C(16)

1,08

1,08

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(19)-C(16)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(20)-F(21)

0,90

0,90

0,90

0,90

0,90

0,90

0,91

0,91

0,91

0,91

H(20)-C(1)

3,10

3,00

2,90

2,80

2,70

2,60

2,50

2,40

2,30

2,20

B(22)-F(21)

2,43

2,42

2,41

2,41

2,40

2,41

2,39

2,38

2,37

2,36

F(23)-B(22)

1,30

1,30

1,30

1,30

1,30

1,31

1,31

1,31

1,31

1,31

F(24)-B(22)

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,30

F(25)-B(22)

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,30

C(26)-C(31)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(27)-C(26)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(28)-C(27)

1,38

1,38

1,38

1,38

1,38

1,39

1,39

1,39

1,39

1,39

C(29)-C(28)

1,39

1,39

1,39

1,39

1,39

1,38

1,38

1,38

1,38

1,38

C(30)-C(29)

1,38

1,38

1,38

1,38

1,38

1,39

1,39

1,39

1,39

1,39

C(31)-C(30)

1,39

1,39

1,39

1,39

1,39

1,38

1,38

1,38

1,38

1,39

C(32)-C(26)

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

H(33)-C(27)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(34)-C(28)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(35)-C(29)

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

H(36)-C(30)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,07

H(37)-C(31)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(38)-C(32)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(39)-C(32)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(40)-C(32)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

Continuation of Table 1.

No of step

11

12

13

14

15

16

17

18

19

20

21

C(2)-C(1)

1,33

1,33

1,33

1,33

1,33

1,33

1,33

1,34

1,46

1,47

1,47

H(3)-C(2)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,07

1,07

1,07

H(4)-C(1)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(5)-C(1)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

C(6)-C(11)

1,40

1,39

1,40

1,39

1,40

1,39

1,40

1,40

1,42

1,42

1,42

C(6)-C(2)

1,48

1,48

1,48

1,48

1,48

1,48

1,47

1,47

1,40

1,40

1,39

C(7)-C(6)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,41

1,41

1,41

C(8)-C(7)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,38

1,38

1,38

1,38

C(9)-C(8)

1,38

1,38

1,38

1,38

1,38

1,39

1,39

1,39

1,39

1,39

1,39

C(10)-C(9)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,40

1,41

1,41

1,41

C(11)-C(10)

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,36

1,36

1,36

H(12)-C(7)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,07

1,07

1,07

H(13)-C(8)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,07

1,07

1,07

H(14)-C(10)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,07

1,07

1,07

H(15)-C(11)

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

C(16)-C(9)

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,50

1,50

1,50

H(17)-C(16)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(18)-C(16)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,08

1,09

1,09

H(19)-C(16)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(20)-F(21)

0,91

0,92

0,92

0,93

0,94

0,95

0,97

1,06

2,51

2,52

2,51

H(20)-C(1)

2,10

2,00

1,90

1,80

1,70

1,60

1,50

1,40

1,30

1,20

1,10

B(22)-F(21)

2,34

2,33

2,30

2,29

2,26

2,22

2,15

1,72

1,41

1,41

1,41

F(23)-B(22)

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,34

1,42

1,42

1,42

F(24)-B(22)

1,30

1,30

1,30

1,30

1,30

1,30

1,31

1,33

1,36

1,36

1,36

F(25)-B(22)

1,30

1,30

1,30

1,30

1,30

1,30

1,30

1,32

1,37

1,37

1,37

C(26)-C(31)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(27)-C(26)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(28)-C(27)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(29)-C(28)

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,39

1,39

1,39

C(30)-C(29)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,38

1,38

1,38

C(31)-C(30)

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,38

1,39

1,39

1,39

C(32)-C(26)

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

1,51

H(33)-C(27)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(34)-C(28)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,07

1,07

1,07

H(35)-C(29)

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

H(36)-C(30)

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,07

1,08

1,08

1,08

H(37)-C(31)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(38)-C(32)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,09

1,09

1,09

H(39)-C(32)

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

1,08

H(40)-C(32)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

Table 2. Change in valence angles along the interaction pathway of complex catalystHF BF3 with p-methylstyrene in toluene (the stoichiometric composition of 1:1:1)

No of step

1

2

3

4

5

6

7

8

9

10

H(3)-C(2)-C(1)

118

118

118

118

118

118

118

118

118

118

H(4)-C(1)-C(2)

121

121

121

120

120

120

121

121

121

121

H(5)-C(1)-C(2)

123

123

123

123

123

123

123

123

122

123

C(6)-C(11)-C(10)

121

121

121

121

121

121

121

121

121

121

C(6)-C(2)-C(1)

127

127

127

127

127

127

127

127

127

127

C(7)-C(6)-C(11)

118

118

118

118

118

118

118

118

118

118

C(8)-C(7)-C(6)

121

121

121

121

121

121

121

121

121

121

C(9)-C(8)-C(7)

121

121

121

121

121

121

121

121

121

121

C(10)-C(9)-C(8)

118

118

118

118

118

118

118

118

118

118

C(11)-C(10)-C(9)

121

121

121

121

121

121

121

121

121

121

H(12)-C(7)-C(6)

120

120

120

120

120

120

120

120

120

120

H(13)-C(8)-C(7)

119

119

119

119

119

119

119

119

119

119

H(14)-C(10)-C(9)

120

120

119

119

119

119

119

119

119

119

H(15)-C(11)-C(10)

119

119

119

119

119

119

119

119

119

119

C(16)-C(9)-C(8)

121

121

122

122

122

122

122

122

122

122

H(17)-C(16)-C(9)

111

111

111

111

111

111

111

111

111

111

H(18)-C(16)-C(9)

111

111

111

111

111

111

111

111

111

111

H(19)-C(16)-C(9)

111

111

111

111

111

111

111

111

111

111

H(20)-F(21)-B(22)

123

123

122

122

123

122

122

122

122

122

H(20)-C(1)-C(2)

69

69

70

72

72

74

74

75

77

79

F(23)-B(22)-F(21)

91

91

91

91

91

91

91

91

91

91

F(24)-B(22)-F(21)

92

92

92

92

92

92

92

92

93

93

F(25)-B(22)-F(21)

94

94

94

94

94

94

94

94

94

94

C(26)-C(31)-C(30)

121

121

121

121

121

121

121

121

121

121

C(27)-C(26)-C(31)

118

118

118

118

118

118

118

118

118

118

C(28)-C(27)-C(26)

121

121

121

121

121

121

121

121

121

121

C(29)-C(28)-C(27)

120

120

120

120

120

120

120

120

120

120

C(30)-C(29)-C(28)

119

119

119

119

119

119

119

119

119

119

C(31)-C(30)-C(29)

120

120

120

120

120

120

120

120

120

120

C(32)-C(26)-C(31)

121

121

121

121

121

121

121

121

121

121

H(33)-C(27)-C(26)

120

120

120

120

120

120

120

120

120

120

H(34)-C(28)-C(27)

120

120

120

120

120

120

120

120

120

120

H(35)-C(29)-C(28)

120

120

120

120

120

120

121

121

121

121

H(36)-C(30)-C(29)

120

120

120

120

120

120

120

120

120

120

H(37)-C(31)-C(30)

119

119

119

119

119

120

119

119

119

119

H(38)-C(32)-C(26)

111

111

111

111

111

111

111

111

111

111

H(39)-C(32)-C(26)

111

111

111

111

111

111

111

111

111

111

H(40)-C(32)-C(26)

111

111

111

111

111

111

111

111

111

111

Continuation of Table 2.

No of step

11

12

13

14

15

16

17

18

19

20

21

H(3)-C(2)-C(1)

118

118

118

118

118

118

118

117

115

115

116

H(4)-C(1)-C(2)

121

121

120

121

120

120

120

120

112

111

110

H(5)-C(1)-C(2)

122

122

123

122

122

122

122

122

117

116

115

C(6)-C(11)-C(10)

121

121

121

121

121

121

121

121

120

120

120

C(6)-C(2)-C(1)

127

127

127

127

127

127

127

128

128

128

128

C(7)-C(6)-C(11)

118

118

118

118

118

118

118

119

119

119

119

C(8)-C(7)-C(6)

121

121

121

121

121

121

121

121

120

120

120

C(9)-C(8)-C(7)

121

121

121

121

121

121

121

121

120

120

120

C(10)-C(9)-C(8)

118

118

118

118

118

118

118

118

120

120

120

C(11)-C(10)-C(9)

121

121

121

121

121

121

121

121

121

121

120

H(12)-C(7)-C(6)

120

120

120

120

120

120

120

120

119

119

119

H(13)-C(8)-C(7)

119

119

119

119

119

119

119

119

120

120

120

H(14)-C(10)-C(9)

119

120

119

119

119

120

120

120

119

119

119

H(15)-C(11)-C(10)

119

119

119

119

119

119

119

119

119

120

120

C(16)-C(9)-C(8)

122

122

122

122

122

121

121

121

121

121

121

H(17)-C(16)-C(9)

111

111

111

111

111

111

111

111

112

112

112

H(18)-C(16)-C(9)

111

111

111

111

111

111

111

111

111

110

110

H(19)-C(16)-C(9)

111

111

111

111

111

111

111

111

110

110

110

H(20)-F(21)-B(22)

122

122

122

123

123

123

124

123

148

148

148

H(20)-C(1)-C(2)

80

81

83

85

87

89

90

88

99

102

103

F(23)-B(22)-F(21)

92

92

92

92

93

93

94

100

106

106

106

F(24)-B(22)-F(21)

93

93

93

93

94

94

95

101

110

110

110

F(25)-B(22)-F(21)

94

94

94

94

94

95

95

102

109

109

109

C(26)-C(31)-C(30)

121

121

121

121

121

121

121

121

121

121

121

C(27)-C(26)-C(31)

118

118

118

118

118

118

118

118

118

118

118

C(28)-C(27)-C(26)

121

121

121

121

121

121

121

121

121

121

121

C(29)-C(28)-C(27)

120

120

120

120

120

120

120

120

120

120

120

C(30)-C(29)-C(28)

119

119

119

119

119

119

119

119

119

119

119

C(31)-C(30)-C(29)

120

120

120

120

120

120

120

120

120

120

120

C(32)-C(26)-C(31)

121

121

121

121

121

121

121

121

121

121

121

H(33)-C(27)-C(26)

120

120

120

120

120

120

120

120

119

119

119

H(34)-C(28)-C(27)

120

120

120

120

120

120

120

120

120

120

120

H(35)-C(29)-C(28)

121

121

121

121

121

121

121

121

120

120

120

H(36)-C(30)-C(29)

120

120

120

120

120

120

120

120

120

120

120

H(37)-C(31)-C(30)

119

119

119

119

119

119

119

119

120

120

120

H(38)-C(32)-C(26)

111

111

111

111

111

111

111

111

111

111

111

H(39)-C(32)-C(26)

111

111

111

111

111

111

111

111

111

111

111

H(40)-C(32)-C(26)

111

111

111

111

111

111

111

111

111

111

111

Table 3.Change in atomic charges along the interaction pathway of complex catalyst HF BF3 with p-methylstyrene in toluene (the stoichiometric composition of 1:1:1)

Atom

1

2

3

4

5

6

7

8

9

10

C(1)

-0,209

-0,212

-0,214

-0,220

-0,226

-0,238

-0,245

-0,257

-0,270

-0,290

C(2)

-0,174

-0,178

-0,177

-0,177

-0,178

-0,177

-0,178

-0,173

-0,168

-0,152

H(3)

0,119

0,120

0,118

0,119

0,121

0,121

0,123

0,124

0,124

0,122

H(4)

0,134

0,136

0,143

0,144

0,146

0,156

0,157

0,159

0,161

0,167

H(5)

0,105

0,106

0,105

0,107

0,108

0,108

0,110

0,112

0,114

0,116

C(6)

-0,054

-0,053

-0,062

-0,059

-0,058

-0,061

-0,060

-0,060

-0,061

-0,065

C(7)

-0,068

-0,067

-0,056

-0,056

-0,056

-0,055

-0,054

-0,052

-0,051

-0,046

C(8)

-0,090

-0,090

-0,084

-0,084

-0,084

-0,084

-0,083

-0,083

-0,083

-0,084

C(9)

-0,120

-0,120

-0,123

-0,122

-0,122

-0,122

-0,122

-0,122

-0,121

-0,121

C(10)

-0,084

-0,084

-0,086

-0,086

-0,086

-0,086

-0,086

-0,086

-0,086

-0,086

C(11)

-0,064

-0,064

-0,060

-0,061

-0,061

-0,060

-0,060

-0,060

-0,060

-0,057

H(12)

0,104

0,105

0,100

0,101

0,102

0,103

0,104

0,104

0,104

0,100

H(13)

0,088

0,088

0,087

0,087

0,088

0,088

0,088

0,088

0,088

0,089

H(14)

0,086

0,086

0,086

0,086

0,087

0,087

0,087

0,088

0,088

0,088

H(15)

0,092

0,092

0,091

0,092

0,092

0,092

0,093

0,093

0,094

0,094

C(16)

-0,177

-0,177

-0,177

-0,177

-0,177

-0,177

-0,177

-0,177

-0,177

-0,177

H(17)

0,100

0,099

0,095

0,095

0,095

0,095

0,095

0,095

0,096

0,096

H(18)

0,098

0,098

0,106

0,106

0,106

0,107

0,107

0,107

0,108

0,108

H(19)

0,114

0,114

0,110

0,110

0,111

0,110

0,110

0,110

0,111

0,110

H(20)

0,346

0,348

0,349

0,351

0,354

0,356

0,360

0,366

0,372

0,378

F(21)

-0,334

-0,336

-0,338

-0,340

-0,344

-0,347

-0,351

-0,356

-0,362

-0,368

B(22)

0,816

0,818

0,815

0,817

0,818

0,820

0,821

0,823

0,825

0,822

F(23)

-0,288

-0,288

-0,288

-0,288

-0,289

-0,290

-0,291

-0,292

-0,293

-0,292

F(24)

-0,273

-0,274

-0,274

-0,275

-0,275

-0,274

-0,274

-0,275

-0,276

-0,278

F(25)

-0,263

-0,263

-0,263

-0,263

-0,264

-0,264

-0,265

-0,265

-0,266

-0,266

C(26)

-0,123

-0,124

-0,123

-0,123

-0,123

-0,118

-0,118

-0,118

-0,118

-0,116

C(27)

-0,098

-0,098

-0,098

-0,099

-0,100

-0,100

-0,100

-0,100

-0,101

-0,100

C(28)

-0,088

-0,088

-0,087

-0,087

-0,087

-0,087

-0,087

-0,087

-0,087

-0,083

C(29)

-0,130

-0,130

-0,126

-0,126

-0,125

-0,126

-0,126

-0,125

-0,124

-0,127

C(30)

-0,100

-0,100

-0,100

-0,099

-0,096

-0,097

-0,095

-0,093

-0,091

-0,093

C(31)

-0,099

-0,099

-0,104

-0,104

-0,105

-0,108

-0,108

-0,109

-0,110

-0,114

C(32)

-0,175

-0,175

-0,174

-0,174

-0,174

-0,175

-0,175

-0,174

-0,174

-0,174

H(33)

0,089

0,089

0,088

0,088

0,088

0,087

0,087

0,087

0,087

0,087

H(34)

0,099

0,098

0,098

0,097

0,097

0,096

0,096

0,096

0,096

0,095

H(35)

0,118

0,118

0,117

0,118

0,117

0,115

0,115

0,115

0,114

0,110

H(36)

0,105

0,105

0,106

0,106

0,106

0,106

0,106

0,107

0,107

0,112

H(37)

0,088

0,088

0,088

0,088

0,088

0,088

0,088

0,088

0,087

0,088

H(38)

0,100

0,100

0,100

0,100

0,099

0,098

0,098

0,097

0,097

0,097

H(39)

0,096

0,096

0,096

0,096

0,096

0,097

0,097

0,097

0,097

0,097

H(40)

0,114

0,114

0,114

0,114

0,114

0,113

0,113

0,113

0,113

0,113

Continuation of Table 3.

Atom

11

12

13

14

15

16

17

18

19

20

21

C(1)

-0,303

-0,315

-0,328

-0,338

-0,347

-0,350

-0,351

-0,369

-0,288

-0,268

-0,245

C(2)

-0,146

-0,138

-0,127

-0,116

-0,101

-0,090

-0,075

-0,022

0,119

0,115

0,110

H(3)

0,124

0,125

0,124

0,125

0,124

0,126

0,129

0,147

0,242

0,239

0,237

H(4)

0,168

0,170

0,174

0,174

0,176

0,176

0,177

0,186

0,181

0,172

0,165

H(5)

0,118

0,121

0,123

0,126

0,128

0,130

0,132

0,138

0,118

0,112

0,106

C(6)

-0,067

-0,070

-0,075

-0,080

-0,086

-0,091

-0,099

-0,133

-0,213

-0,211

-0,211

C(7)

-0,046

-0,044

-0,042

-0,040

-0,038

-0,035

-0,031

-0,008

0,067

0,069

0,069

C(8)

-0,083

-0,084

-0,084

-0,084

-0,084

-0,085

-0,085

-0,088

-0,113

-0,111

-0,110

C(9)

-0,120

-0,120

-0,119

-0,118

-0,117

-0,116

-0,114

-0,105

-0,054

-0,054

-0,053

C(10)

-0,086

-0,086

-0,086

-0,087

-0,087

-0,088

-0,088

-0,092

-0,114

-0,114

-0,115

C(11)

-0,057

-0,057

-0,054

-0,054

-0,050

-0,049

-0,046

-0,032

0,021

0,022

0,023

H(12)

0,101

0,101

0,100

0,101

0,100

0,101

0,103

0,112

0,181

0,178

0,178

H(13)

0,089

0,090

0,090

0,090

0,091

0,091

0,092

0,097

0,119

0,119

0,119

H(14)

0,088

0,089

0,089

0,090

0,090

0,091

0,092

0,095

0,108

0,108

0,108

H(15)

0,095

0,095

0,096

0,096

0,097

0,098

0,099

0,103

0,120

0,122

0,123

C(16)

-0,178

-0,178

-0,178

-0,178

-0,178

-0,178

-0,178

-0,180

-0,186

-0,186

-0,186

H(17)

0,096

0,096

0,096

0,096

0,097

0,097

0,098

0,101

0,118

0,118

0,118

H(18)

0,108

0,108

0,109

0,109

0,110

0,110

0,111

0,113

0,122

0,124

0,125

H(19)

0,111

0,111

0,111

0,112

0,112

0,113

0,114

0,118

0,136

0,135

0,135

H(20)

0,385

0,392

0,398

0,404

0,406

0,407

0,407

0,416

0,207

0,202

0,195

F(21)

-0,375

-0,383

-0,391

-0,400

-0,410

-0,423

-0,440

-0,441

-0,471

-0,472

-0,472

B(22)

0,825

0,828

0,829

0,832

0,834

0,839

0,847

0,860

0,866

0,866

0,866

F(23)

-0,294

-0,295

-0,297

-0,299

-0,301

-0,305

-0,311

-0,364

-0,471

-0,470

-0,470

F(24)

-0,278

-0,279

-0,280

-0,282

-0,283

-0,285

-0,290

-0,326

-0,389

-0,389

-0,389

F(25)

-0,267

-0,268

-0,269

-0,270

-0,272

-0,274

-0,278

-0,316

-0,412

-0,412

-0,411

C(26)

-0,117

-0,117

-0,116

-0,116

-0,115

-0,115

-0,116

-0,117

-0,122

-0,121

-0,121

C(27)

-0,101

-0,101

-0,101

-0,101

-0,101

-0,101

-0,102

-0,103

-0,124

-0,121

-0,121

C(28)

-0,084

-0,085

-0,084

-0,085

-0,085

-0,086

-0,087

-0,090

-0,113

-0,111

-0,112

C(29)

-0,125

-0,126

-0,128

-0,128

-0,128

-0,129

-0,130

-0,132

-0,123

-0,124

-0,124

C(30)

-0,089

-0,088

-0,089

-0,088

-0,088

-0,087

-0,086

-0,094

-0,093

-0,093

-0,093

C(31)

-0,114

-0,114

-0,115

-0,115

-0,115

-0,115

-0,115

-0,114

-0,109

-0,110

-0,109

C(32)

-0,174

-0,174

-0,175

-0,174

-0,175

-0,175

-0,175

-0,174

-0,171

-0,172

-0,172

H(33)

0,086

0,086

0,086

0,086

0,086

0,086

0,085

0,085

0,084

0,084

0,084

H(34)

0,095

0,095

0,095

0,095

0,095

0,094

0,094

0,094

0,125

0,125

0,125

H(35)

0,109

0,108

0,107

0,107

0,107

0,107

0,108

0,115

0,150

0,148

0,148

H(36)

0,112

0,112

0,114

0,115

0,115

0,116

0,118

0,125

0,100

0,099

0,099

H(37)

0,088

0,088

0,088

0,088

0,088

0,088

0,088

0,088

0,084

0,083

0,083

H(38)

0,097

0,097

0,096

0,096

0,096

0,096

0,096

0,095

0,092

0,092

0,092

H(39)

0,097

0,097

0,098

0,098

0,098

0,098

0,098

0,097

0,092

0,092

0,092

H(40)

0,113

0,113

0,113

0,113

0,113

0,113

0,113

0,113

0,114

0,114

0,114

References

  1. Cirelson V.G., Quantum Chemistry. Molecules, molecular systems and solids, Binom Publishing House, Moscow, 2010, 496 (in Russian).
  2. Granovsky A. A., Firefly version 8, 2013. http://classic.chem.msu.su/gran/firefly/index.html
  3. Schmidt M.W. et al., General atomic and molecular electronic structure system, J. Comput. Chem. 1993, 14, 1347-1363.
  4. Babkin V.A. et al., Potential energy surface of interaction between ethriolbicyclophosphite and acetyl chloride (second stage), Oxidation Communications, 2018, 41(2), 231-239.
  5. Babkin V.A. et al., On the cationic polymerization mechanism p-isopropylstyrene in the presence of a complex catalyst boron fluoride-water, Oxidation Communications, 2019, 42(1), 56‑62.
  6. Babkin V.A. et al., Quantum-chemical study of protonation mechanism of 2,3,4,5-teramethylstyrene by AB INITIO method, Bulletin of Volgograd State Technical University, 2019, 5(228), 22-28 (in Russian).
  7. Babkin V.A. et al., About the mechanism of cationic polymerization of p-ethylstyrene in the presence of a complex catalyst boron fluoride–water, Fluorine Notes, 2019, 3(124), 3-4.
  8. Babkin V.A. et al., Quantum chemical investigation of initiation mechanism for cationic polymerisation of 4-methylpentene-1 with chloride–aluminum aquacomplex, Oxidation Communications, 2019, 42 (3), 275–281.
  9. B.M. Bode, M.S. Gordon, MacMolPlt: A Graphical User Interface for GAMESS, Journal of Molecular Graphics, 1998, 16, 133-138.

ARTICLE INFO
Received 08 February 2021
Accepted 25 February 2021
Available online April 2021

Recommended for publication by Prof. S.M. Igumnov

Fluorine Notes, 2021, 135, 3-4

Back to volume # 2(135) , March - April 2021
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