The publication of the journal is supported by
SIA "P&M-Invest" Ltd and INEOS RAS
Volume # 4(125), July - August 2019 — "Quantum-Chemical Study of the Protonation Mechanism of P-Fluorostyrol by the MNDO Method"
Received: March 2019

DOI 10.17677/fn20714807.2019.04.03

Fluorine Notes, 2019, 125, 5-6

QUANTUM-CHEMICAL STUDY OF THE PROTONATION MECHANISM OF p-FLUORSTYROL BY THE MNDO METHOD

V.A. Babkin1, Yu. A. Vashuta1, A.V. Kozhukhova1, D.S. Andreev1, A.V. Ignatov1, A.P. Knyazev1, A.I. Rakhimov2, E.S. Titova2,3, V.S. Belousova4, A.R. Denisyuk5, K.Yu. Prochukhan6, O.S. Rakhimova7

1Sebryakovsky branch of the Volgograd State Technical University, 403343 Volgograd Region, Mikhaylovka, Michurin Street, 21
e-mail: babkin_v.a@mail.ru

2Volgograd State Technical University, 400005 Volgograd, Lenin Avenue, 28
e-mail: organic@vstu.ru

3Volgograd State Medical University, 400131 Volgograd, Pavshich bortcov Square, 1
4 I.M. Sechenov First Moscow State Medical University (Sechenov University) , 119991, Moscow, Trubeckaya Street, 8, building 2
5Medical College of Volgograd State Medical University, 400001 Volgograd, Kim Street, 18
6Bashkir State University, 450076, Republic of Bashkortostan, Ufa, Zaki Validi Street, 32
7Volgograd State University, 400062, Volgograd, University Avenue, 100

Abstract: The mechanism of protonation of p-fluorstyrol first studied by classical quantum-chemical method MNDO. This mechanism is a reaction of the electrophilic addition of a proton to the double bond of a monomer. The reaction is exothermic and has no barrier character. The gain of energy as a result of the reaction in the attack on the α-carbon atom is -540 kJ/mol. The reaction follows the classical scheme in accordance with Markovnikov rule.

Keywords: protonation mechanism, MNDO method, p-fluorostyrene, Markovnikov rule.

Study of the mechanism of protonation of p-fluorstyrol [1] is the first step in the study of the mechanism of cationic polymerization of this monomer. Тhe aim of the present work is a quantum-chemical study of the mechanism of protonation of p-fluorstyrol by classical semi-empirical method MNDO.

Methodical Part

The methodology for studying the protonation mechanism of p-fluorostyrene is completely consistent with the method used to study the mechanism for the protonation of p-ethylstyrene [2-4]. 17 Atoms are in the system H+ ... C8H7F. M = 2S + 1 = 1 (S is the total spin of all electrons of the system under study is equal to zero. All electrons are paired. M-multiplicity). The total charge of the molecular system is ∑ qc = 1. The reaction coordinates were the distances from the proton H1 to C2 (RH1C2) and from H1 to C3 (RH1C3). The equipotential surface of the interactions of the proton with the p-fluorosterene was constructed according to the data obtained, the energy values along the reaction coordinates (Fig. 4.). The initial model of the proton attack of the p-fluorostyrene molecule is shown in Fig. 1.

Fig. 1. The initial model of the attack of proton of the molecule p-fluorothyrene.

For the visual presentation of molecular models was used the well-known program MacMolPlt [5].

Results and Discussion

The structure of the formed carbocation (I) after the attack of the proton H1 of the α – carbon atom of p-fluorostyrene (C2) and the rupture of the double bond of p-fluorothyrene is shown in Fig. 2. The structure of the formed carbocation (II) after the attack of the proton H1 β – carbon atom of p-fluorostyrene (C3) and the breaking of the double bond C2 = C3 is shown in Fig. 3. The charges on the carbocation atoms (I) and (II) are presented in Table. 1. The change in total energy during protonation of p-fluorostyrene is shown in Fig. 4. Negative values ​​of the total energy of the system H+ ... C8H7F (Е0) increases along the entire path of motion of the initiating particle H+ along the coordinates of the reaction RH1С2 and RH1С3. The energy barrier is absent both when attacking α- and β-carbon atoms of p-fluorostyrene. Structure (I) at 68 kJ/mol is energetically more favorable than (II). This is in full accordance with the classical Markovnikov rule. The energy gain due to the formation of (I) is 540 kJ/mol, and during the formation of (II) 472 kJ/mol.

Analysis of the results of quantum chemical calculations, the changes of bond lengths and valence angles along the reaction coordinate during the attack of the proton on the α- and β-carbon atoms of a p-fluorostyrene suggests that the mechanism of protonation of the cationic polymerization of p-fluorostyrene goes according to the classical scheme of addition of the proton to the double bond of the monomer.

Thus, we first studied the mechanism of protonation of p-fluorostyrene quantum-chemical method MNDO. It is shown that this mechanism is a usual reaction of the proton addition to the olefin double bond. The reaction is exothermic and barrier-free. The reactions are energetically advantageous to follow the classical scheme in accordance with the Markovnikov rule.

Fig.2. The structure of the formed carbocation (I) after the attack of the proton H1 of the α - carbon atom of p-fluorostyrene (C2)

Fig.3. - The structure of the formed carbocation (II) after the attack of the proton H1 of the β– carbon atom of p-fluorostyrene (С3)

Fig. 4. Potential surface of the energy of the interactions of the proton with p-fluorostyrene.

Fig. 5. The change in total energy at the accession of the proton H1 to the α–carbon atom of p-fluorostyrene

Table 1. Changes in bond lengths along the path of the H1 proton addition reaction to the α-carbon atom of a p-fluorostyrene

Step number

1

2

3

4

5

6

7

8

9

10

C(2)-H(1)

3,10

3,00

2,90

2,80

2,70

2,60

2,50

2,40

2,30

2,20

C(3)-H(1)

3,10

3,00

3,00

3,00

2,90

2,90

2,90

2,80

2,80

2,70

C(3)-C(2)

1,38

1,38

1,38

1,39

1,39

1,39

1,40

1,40

1,41

1,41

C(4)-C(3)

1,44

1,44

1,44

1,44

1,44

1,43

1,43

1,43

1,43

1,42

C(5)-C(4)

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

C(6)-C(5)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(7)-C(4)

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

C(8)-C(9)

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

C(8)-C(6)

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

C(9)-C(7)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

F(10)-C(8)

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

H(11)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(12)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(13)-C(3)

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

H(14)-C(7)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(15)-C(9)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(16)-C(6)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(17)-C(5)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

Continuation of table 1

Step number

11

12

13

14

15

16

17

18

19

20

21

C(2)-H(1)

2,10

2,00

1,90

1,80

1,70

1,60

1,50

1,40

1,30

1,20

1,10

C(3)-H(1)

2,70

2,60

2,60

2,60

2,50

2,50

2,50

2,40

2,40

2,30

2,20

C(3)-C(2)

1,42

1,43

1,43

1,45

1,45

1,46

1,48

1,48

1,49

1,49

1,49

C(4)-C(3)

1,42

1,42

1,41

1,41

1,41

1,40

1,40

1,40

1,39

1,39

1,39

C(5)-C(4)

1,44

1,44

1,45

1,45

1,45

1,45

1,45

1,45

1,45

1,45

1,45

C(6)-C(5)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(7)-C(4)

1,45

1,45

1,45

1,45

1,45

1,45

1,46

1,46

1,46

1,46

1,46

C(8)-C(9)

1,43

1,43

1,43

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

C(8)-C(6)

1,43

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

C(9)-C(7)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

F(10)-C(8)

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

H(11)-C(2)

1,09

1,09

1,09

1,09

1,09

1,10

1,10

1,10

1,11

1,11

1,11

H(12)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,10

1,10

1,11

1,11

1,11

H(13)-C(3)

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

H(14)-C(7)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(15)-C(9)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(16)-C(6)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(17)-C(5)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

Table 2. Changes in the valence angles along the reaction path for the addition of the proton H1 to the α – carbon atom of p-fluorostyrene

step number

1

2

3

4

5

6

7

8

9

10

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

77

77

80

84

84

88

92

91

95

94

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

77

77

72

68

68

64

60

59

55

54

C(4)-C(3)-C(2)

129

129

129

129

129

129

129

129

129

129

C(5)-C(4)-C(3)

124

124

124

124

124

124

124

124

124

124

C(6)-C(5)-C(4)

122

122

122

122

122

122

122

122

122

122

C(7)-C(4)-C(3)

119

119

119

119

119

119

119

119

119

119

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

120

120

120

120

120

120

120

120

120

120

C(8)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

C(9)-C(7)-C(4)

122

122

122

122

122

122

122

122

122

122

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

120

120

120

120

120

120

120

120

120

120

H(11)-C(2)-C(4)

99

99

99

99

99

99

99

99

99

98

H(12)-C(2)-C(4)

147

147

147

147

147

146

146

146

145

145

H(13)-C(3)-C(2)

116

116

115

115

115

115

115

115

115

115

H(14)-C(7)-C(4)

120

120

120

120

120

120

120

120

120

120

H(15)-C(9)-C(7)

120

120

120

120

120

120

120

120

120

120

H(16)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

H(17)-C(5)-C(4)

120

120

120

120

120

120

120

120

120

120

Continuation of table 2

Step number

11

12

13

14

15

16

17

18

19

20

21

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

98

97

102

106

105

109

114

113

118

117

115

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

50

50

46

42

41

37

33

33

28

28

27

C(4)-C(3)-C(2)

129

129

129

129

129

129

129

129

130

130

130

C(5)-C(4)-C(3)

124

124

124

124

124

124

124

124

124

124

124

C(6)-C(5)-C(4)

122

122

122

122

122

122

122

122

122

122

122

C(7)-C(4)-C(3)

119

119

119

119

119

119

120

120

119

119

119

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

120

120

120

120

120

120

120

120

120

120

120

C(8)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

120

C(9)-C(7)-C(4)

122

122

122

122

122

122

122

122

122

122

122

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

120

120

120

120

120

120

120

120

120

120

120

H(11)-C(2)-C(4)

98

98

97

97

96

138

137

136

121

120

120

H(12)-C(2)-C(4)

144

143

142

140

139

95

95

95

119

120

120

H(13)-C(3)-C(2)

114

114

114

114

114

113

113

113

112

112

112

H(14)-C(7)-C(4)

119

119

119

119

119

119

119

119

119

119

119

H(15)-C(9)-C(7)

120

120

120

120

120

120

120

120

120

120

120

H(16)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

120

H(17)-C(5)-C(4)

120

120

120

120

120

120

120

120

120

120

120

Table 3. Changes in charges along the path of the proton H1 addition reaction to the α – carbon atom of p-fluorostyrene

Atom

1

2

3

4

5

6

7

8

9

10

H(1)

0,388

0,377

0,369

0,360

0,344

0,332

0,318

0,296

0,279

0,254

C(2)

0,059

0,061

0,048

0,033

0,032

0,015

-0,003

-0,007

-0,028

-0,032

C(3)

-0,011

-0,002

0,016

0,037

0,050

0,074

0,099

0,117

0,144

0,163

C(4)

-0,102

-0,111

-0,119

-0,128

-0,138

-0,148

-0,158

-0,169

-0,179

-0,190

C(5)

0,032

0,037

0,041

0,046

0,051

0,058

0,065

0,071

0,079

0,086

C(6)

-0,108

-0,109

-0,112

-0,114

-0,116

-0,118

-0,122

-0,124

-0,127

-0,130

C(7)

0,048

0,051

0,056

0,062

0,066

0,072

0,078

0,083

0,090

0,096

C(8)

0,288

0,290

0,293

0,297

0,300

0,304

0,309

0,314

0,320

0,326

C(9)

-0,111

-0,113

-0,114

-0,116

-0,118

-0,121

-0,123

-0,126

-0,129

-0,132

F(10)

-0,124

-0,124

-0,124

-0,124

-0,124

-0,123

-0,122

-0,121

-0,120

-0,118

H(11)

0,075

0,077

0,077

0,077

0,079

0,080

0,080

0,082

0,082

0,083

H(12)

0,081

0,082

0,083

0,083

0,085

0,086

0,086

0,088

0,088

0,090

H(13)

0,082

0,082

0,083

0,084

0,084

0,084

0,085

0,086

0,086

0,086

H(14)

0,089

0,089

0,089

0,089

0,089

0,090

0,090

0,090

0,091

0,092

H(15)

0,117

0,117

0,117

0,118

0,118

0,118

0,119

0,120

0,121

0,122

H(16)

0,115

0,115

0,116

0,116

0,116

0,117

0,118

0,118

0,119

0,120

H(17)

0,081

0,081

0,080

0,080

0,080

0,081

0,081

0,082

0,083

0,084

Continuation of table 3

Atom

11

12

13

14

15

16

17

18

19

20

21

H(1)

0,234

0,207

0,187

0,169

0,145

0,132

0,120

0,103

0,053

0,048

0,042

C(2)

-0,053

-0,056

-0,074

-0,086

-0,081

-0,083

-0,080

-0,066

-0,049

-0,036

-0,023

C(3)

0,191

0,208

0,232

0,250

0,258

0,268

0,273

0,272

0,270

0,265

0,261

C(4)

-0,199

-0,208

-0,214

-0,219

-0,224

-0,226

-0,227

-0,228

-0,226

-0,226

-0,226

C(5)

0,095

0,102

0,111

0,120

0,126

0,132

0,136

0,139

0,146

0,146

0,145

C(6)

-0,134

-0,137

-0,141

-0,145

-0,148

-0,151

-0,153

-0,154

-0,158

-0,157

-0,157

C(7)

0,103

0,109

0,116

0,122

0,126

0,131

0,135

0,138

0,139

0,139

0,139

C(8)

0,334

0,341

0,350

0,359

0,366

0,373

0,379

0,383

0,388

0,388

0,388

C(9)

-0,136

-0,138

-0,142

-0,146

-0,148

-0,151

-0,154

-0,155

-0,156

-0,156

-0,156

F(10)

-0,116

-0,114

-0,112

-0,110

-0,108

-0,106

-0,104

-0,103

-0,101

-0,101

-0,101

H(11)

0,082

0,082

0,079

0,075

0,072

0,077

0,069

0,066

0,072

0,071

0,070

H(12)

0,090

0,091

0,089

0,085

0,083

0,067

0,062

0,060

0,073

0,071

0,070

H(13)

0,086

0,087

0,086

0,086

0,087

0,087

0,088

0,088

0,088

0,087

0,086

H(14)

0,093

0,094

0,095

0,096

0,097

0,098

0,100

0,100

0,101

0,100

0,100

H(15)

0,123

0,124

0,125

0,126

0,127

0,128

0,129

0,130

0,131

0,131

0,131

H(16)

0,121

0,122

0,124

0,125

0,126

0,128

0,129

0,129

0,130

0,130

0,130

H(17)

0,086

0,087

0,090

0,092

0,094

0,096

0,097

0,098

0,100

0,100

0,100

Fig. 6. Change of charges on some atoms when the proton H1 is attached to the α – carbon atom of p-fluorostyrene

Fig. 7. The change in total energy when the proton H1 is attached to the β – carbon atom of p-fluoropyrene


Table 4. Change in bond lengths when the proton H1 is attached to the β – carbon atom of p-fluoropyrene

Step number

1

2

3

4

5

6

7

8

9

10

11

C(2)-H(1)

3,10

3,00

2,90

2,80

2,70

2,60

2,60

2,50

2,50

2,50

2,40

C(3)-H(1)

3,10

3,10

3,00

2,90

2,80

2,70

2,60

2,50

2,40

2,30

2,20

C(2)-C(4)

2,54

2,55

2,55

2,55

2,55

2,55

2,55

2,56

2,56

2,56

2,57

C(3)-C(2)

1,38

1,38

1,38

1,39

1,39

1,39

1,39

1,40

1,40

1,40

1,40

C(4)-C(3)

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

C(5)-C(4)

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,43

1,43

1,43

C(6)-C(5)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

C(7)-C(4)

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,44

1,43

C(8)-C(9)

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

C(8)-C(6)

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

C(9)-C(7)

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,39

1,40

1,40

F(10)-C(8)

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

1,31

H(11)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(12)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(13)-C(3)

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

1,10

H(14)-C(7)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(15)-C(9)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(16)-C(6)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(17)-C(5)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

Continuation of table 4

Step number

12

13

14

15

16

17

18

19

20

21

22

C(2)-H(1)

2,40

2,40

2,40

2,30

2,30

2,30

2,30

2,30

2,30

2,30

2,30

C(3)-H(1)

2,10

2,00

1,90

1,80

1,70

1,60

1,50

1,40

1,30

1,20

1,10

C(2)-C(4)

2,57

2,57

2,57

2,57

2,56

2,55

2,54

2,53

2,52

2,51

1,59

C(3)-C(2)

1,41

1,41

1,41

1,42

1,42

1,43

1,44

1,45

1,46

1,48

1,50

C(4)-C(3)

1,45

1,45

1,46

1,47

1,47

1,48

1,49

1,50

1,50

1,51

1,60

C(5)-C(4)

1,43

1,43

1,42

1,42

1,42

1,42

1,42

1,42

1,42

1,42

1,47

C(6)-C(5)

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,38

C(7)-C(4)

1,43

1,43

1,43

1,42

1,42

1,42

1,42

1,42

1,42

1,42

1,47

C(8)-C(9)

1,43

1,43

1,43

1,42

1,42

1,42

1,42

1,42

1,42

1,42

1,44

C(8)-C(6)

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,43

1,44

C(9)-C(7)

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,40

1,38

F(10)-C(8)

1,31

1,31

1,32

1,32

1,32

1,32

1,32

1,32

1,32

1,32

1,30

H(11)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,10

H(12)-C(2)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,10

H(13)-C(3)

1,10

1,10

1,10

1,10

1,10

1,11

1,11

1,11

1,12

1,13

1,10

H(14)-C(7)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(15)-C(9)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(16)-C(6)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

H(17)-C(5)

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

1,09

Table 5. Change in valence angles when the proton H1 is attached to the β – carbon atom of p-fluoropyrene

Step number

1

2

3

4

5

6

7

8

9

10

11

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

77

73

72

72

71

71

74

74

77

81

80

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

77

81

80

80

79

79

74

74

70

65

65

C(3)-C(2)-C(4)

26

26

26

26

26

26

26

26

26

26

26

C(4)-C(3)-C(2)

129

129

129

129

129

129

129

129

129

129

129

C(5)-C(4)-C(3)

124

124

124

124

124

124

124

124

124

124

124

C(6)-C(5)-C(4)

122

122

122

122

122

122

122

122

122

122

122

C(7)-C(4)-C(3)

119

119

119

119

119

119

119

119

119

119

119

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

120

120

120

120

120

120

120

120

120

120

120

C(8)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

120

C(9)-C(7)-C(4)

122

122

122

122

122

122

122

122

122

122

122

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

120

120

120

120

120

120

120

120

120

120

120

H(11)-C(2)-C(4)

99

99

99

99

99

99

99

99

99

99

99

H(12)-C(2)-C(4)

147

147

147

147

147

147

147

146

146

146

146

H(13)-C(3)-C(2)

116

116

115

115

115

115

115

115

115

115

115

H(14)-C(7)-C(4)

120

120

120

120

120

120

120

120

120

120

120

H(15)-C(9)-C(7)

120

120

120

120

120

120

120

120

120

120

120

H(16)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

120

H(17)-C(5)-C(4)

120

120

120

120

120

120

120

120

120

120

120

Continuation of table 5

Step number

12

13

14

15

16

17

18

19

20

21

22

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

84

88

92

90

94

99

103

108

113

118

124

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

60

56

52

51

47

43

39

35

31

27

23

C(3)-C(2)-C(4)

26

27

27

27

28

29

30

31

32

33

62

C(4)-C(3)-C(2)

128

128

127

126

124

122

120

118

117

115

62

C(5)-C(4)-C(3)

124

124

123

123

123

122

122

121

121

120

118

C(6)-C(5)-C(4)

122

122

122

122

122

122

121

121

121

121

123

C(7)-C(4)-C(3)

119

119

119

119

119

120

120

120

120

121

118

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

120

120

120

120

120

120

120

120

120

120

120

C(8)-C(6)-C(5)

120

120

120

120

120

120

120

120

119

120

120

C(9)-C(7)-C(4)

122

122

122

122

122

121

121

121

121

121

123

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

120

120

120

120

120

120

120

120

120

120

120

H(11)-C(2)-C(4)

98

98

97

97

96

95

94

92

91

91

117

H(12)-C(2)-C(4)

147

147

147

148

148

149

150

151

153

152

117

H(13)-C(3)-C(2)

115

115

115

115

115

114

113

112

109

103

119

H(14)-C(7)-C(4)

120

120

120

120

120

120

120

120

120

120

119

H(15)-C(9)-C(7)

120

120

120

120

120

120

120

120

120

120

120

H(16)-C(6)-C(5)

120

120

120

120

120

120

120

120

120

120

120

H(17)-C(5)-C(4)

120

120

120

120

120

120

120

120

120

120

119

Table 6. Charge change when the proton H1 is attached to the β – carbon atom of p-fluoropyrene

Atom

1

2

3

4

5

6

7

8

9

10

11

H(1)

0,388

0,382

0,369

0,355

0,339

0,321

0,318

0,299

0,297

0,297

0,279

C(2)

0,059

0,047

0,048

0,048

0,049

0,050

0,071

0,075

0,101

0,130

0,140

C(3)

-0,011

0,006

0,016

0,028

0,041

0,055

0,044

0,059

0,047

0,034

0,046

C(4)

-0,102

-0,110

-0,119

-0,129

-0,140

-0,151

-0,154

-0,166

-0,169

-0,174

-0,186

C(5)

0,032

0,037

0,041

0,046

0,050

0,055

0,053

0,056

0,053

0,048

0,049

C(6)

-0,108

-0,110

-0,112

-0,113

-0,114

-0,116

-0,114

-0,115

-0,113

-0,110

-0,110

C(7)

0,048

0,052

0,056

0,060

0,065

0,069

0,067

0,071

0,068

0,065

0,067

C(8)

0,288

0,291

0,293

0,296

0,298

0,300

0,298

0,299

0,294

0,288

0,287

C(9)

-0,111

-0,113

-0,114

-0,116

-0,118

-0,119

-0,118

-0,119

-0,117

-0,115

-0,115

F(10)

-0,124

-0,124

-0,124

-0,124

-0,124

-0,124

-0,124

-0,124

-0,126

-0,128

-0,128

H(11)

0,075

0,075

0,077

0,079

0,081

0,083

0,085

0,087

0,089

0,092

0,094

H(12)

0,081

0,082

0,083

0,084

0,086

0,088

0,089

0,091

0,092

0,093

0,095

H(13)

0,082

0,082

0,083

0,084

0,084

0,085

0,086

0,087

0,088

0,089

0,091

H(14)

0,089

0,089

0,089

0,089

0,089

0,088

0,088

0,087

0,086

0,085

0,084

H(15)

0,117

0,117

0,117

0,117

0,118

0,118

0,118

0,118

0,117

0,116

0,116

H(16)

0,115

0,115

0,116

0,116

0,116

0,117

0,116

0,117

0,116

0,115

0,115

H(17)

0,081

0,081

0,080

0,080

0,080

0,080

0,079

0,079

0,077

0,075

0,074

Continuation of table 6

Atom

12

13

14

15

16

17

18

19

20

21

22

H(1)

0,281

0,286

0,292

0,272

0,271

0,261

0,243

0,221

0,194

0,147

0,088

C(2)

0,177

0,217

0,261

0,284

0,334

0,384

0,430

0,470

0,498

0,512

0,074

C(3)

0,030

0,010

-0,014

-0,011

-0,040

-0,068

-0,090

-0,102

-0,102

-0,080

0,070

C(4)

-0,190

-0,195

-0,198

-0,203

-0,202

-0,201

-0,202

-0,205

-0,212

-0,215

-0,278

C(5)

0,042

0,032

0,019

0,015

0,003

-0,004

-0,006

-0,004

0,000

0,002

0,170

C(6)

-0,106

-0,101

-0,095

-0,092

-0,086

-0,082

-0,081

-0,081

-0,081

-0,082

-0,176

C(7)

0,062

0,056

0,050

0,049

0,041

0,033

0,027

0,020

0,015

0,014

0,171

C(8)

0,278

0,267

0,255

0,251

0,240

0,232

0,228

0,226

0,225

0,226

0,423

C(9)

-0,111

-0,106

-0,101

-0,098

-0,093

-0,088

-0,086

-0,084

-0,084

-0,084

-0,176

F(10)

-0,131

-0,134

-0,137

-0,138

-0,141

-0,143

-0,144

-0,145

-0,145

-0,144

-0,093

H(11)

0,097

0,100

0,103

0,106

0,108

0,110

0,111

0,112

0,114

0,115

0,084

H(12)

0,096

0,097

0,098

0,100

0,101

0,102

0,102

0,102

0,102

0,104

0,084

H(13)

0,094

0,097

0,102

0,105

0,110

0,114

0,118

0,121

0,128

0,135

0,080

H(14)

0,083

0,081

0,080

0,079

0,078

0,076

0,075

0,073

0,071

0,070

0,106

H(15)

0,115

0,114

0,112

0,112

0,110

0,109

0,109

0,108

0,108

0,108

0,134

H(16)

0,114

0,112

0,110

0,109

0,108

0,107

0,107

0,106

0,107

0,107

0,134

H(17)

0,070

0,067

0,063

0,061

0,058

0,058

0,059

0,061

0,063

0,066

0,106

Fig. 8 - Change of charges on some atoms along the path of the addition of the proton H1 to the β – carbon atom of p-fluorostyrene

References

  1. Kennedy J. Cationic polymerization of olefins. Moscow, 1978, 431 p.
  2. Babkin V.A., Ignatov A.V., Andreev D.S., Prochukhan K.Yu.,  Stoyanov O.V., Zaikov G.E. Potential interaction surface of proton and p-ethylstyrene. Bulletin of the Technological University, 2016, 19(14), 9-11.
  3. Granovsky Alex A., Firefly version 8. http://classic.chem.msu.su/gran/firefly/index.html
  4. Schmidt M. W., Baldridge K. K., Boatz J. A., Elbert S. T., Gordon M. S, Jensen J. H., Koseki S., Matsunaga N., Nguyen K. A., Su S. J., Windus T. L., Dupuis M., Montgomery J. A. General Atomic and Molecular Electronic Structure System. Journal of Computational Chemistry, 1993, 14, 1347-1363. doi:10.1002/jcc.540141112.
  5. Bode B. M. and M. S. Gordon. MacMolPlt: A Graphical User Interface for GAMESS. Journal of Molecular Graphics. 1998, 16, 133-138.

ARTICLE INFO
Received 19 March 2019
Accepted 16 May 2019
Available online August 2019

Recommended for publication by Prof. S.M. Igumnov

Fluorine Notes, 2019, 125, 5-6

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