Initial Product-Ion Distributions in Ion-Molecule Reactions of CHより_5+, C_2H_5+, and C_3H_5+ with PhX (X = H, CH_3, C_2H_5, C_2H_3, and C_2H)

1)

2)

3)

4)

5)

6)

7)

8)

9)

10)

11)

12)

13)

M. Tsuji, E. Oda, and Y. Nishimura, Chem. Lett., 26,

781 (1997).

M. Tsuji and Y. Nishimura, Bull. Chem. Soc. Jpn., 71,

273 (1998).

M. Tsuji, K. Arikawa, and Y. Nishimura, Bull. Chem.

Soc. Jpn., 72, 293 (1999).

M. Tsuji, T. Arikawa, and Y. Nishimura, Bull. Chem.

Soc. Jpn., 73, 131 (2000).

M. Tsuji, T. Arikawa, Y. Tanaka, and Y. Nishimura,

Bull. Chem. Soc. Jpn., 73, 1673 (2000).

M. Tsuji, T. Arikawa, Y. Tanaka, K. Mogi, and Y.

Sakai, J. Mass Spectrom. Soc. Jpn., 49, 188 (2001).

T. Arikawa and M. Tsuji, J. Mass Spectrom. Soc. Jpn.,

59, 69 (2011).

F. H. Field and M. S. B. Munson, J Am. Chem. Soc.,

87, 3289 (1965).

J. F. J. Todd, R. M. Waldren, and R. F. Bonner, Int. J.

Mass Spectrom. Ion Phys., 34, 17 (1980).

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Mass Spectrom. Ion Phys., 12, 411 (1973).

S. G. Lias, J. E. Bartmess, J. F. Liebman, J. L. Holmes,

R. D. Levin, and W. G. Mallard, J. Phys. Chem. Ref.

Data, 17, Suppl. 1 (1988); updated data were obtained

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(http://webbook.nist.gov/chemistry).

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Ion Process., 134, 73 (1994).

令和 2 年度

九州大学大学院総合理工学報告

第 41 巻

第2号

Appendix

Table A1. Heats of reactions of each product channel (in eV Units).a)

ΣΔH0

ΣΔH0

Reactants

Reactants

CH5+ + PhH

C2H5+ + PhH

C3H5+ + PhH

10.23

10.21

10.66

CH5+ + PhCH3

9.89

C2H5+ + PhCH3

9.87

C3H5+ + PhCH3

10.32

CH5+ + PhC2H5

9.67

C2H5+ + PhC2H5

9.65

C3H5+ + PhC2H5

10.10

Products

(M+ H)+ + CH4

(M + H)+ + C2H4

(M + H)+ + C3H4

(M + C3H5)+

(M + C3H5)+ = PhCH2+

(M + C3H5)+ = C7H7+

o-(M + H)+ + CH4

m-(M + H)+ + CH4

p-(M + H)+ + CH4

i-(M + H)+ + CH4

(M + H)+(exp.) + CH4

o-(M + H)+ + C2H4

m-(M + H)+ + C2H4

p-(M + H)+ + C2H4

i-(M + H)+ + C2H4

(M + H)+(exp.) + C2H4

o-(M + H)+ + C3H4

m-(M + H)+ + C3H4

p-(M + H)+ + C3H4

i-(M + H)+ + C3H4

(M + H)+(exp.) + C3H4

o-(M + C3H5)+

m-(M + C3H5)+

p-(M + C3H5)+

i-(M + C3H5)+

o-CH3C6H4CH2+ + C2H4

m-CH3C6H4CH2+ + C2H4

p-CH3C6H4CH2+ + C2H4

C7H6CH3+ + C2H4

PhCH2+ + C3H6

C7H7+ + C3H6

o-(M + H)+ + CH4

m-(M + H)+ + CH4

p-(M + H)+ + CH4

i-(M + H)+ + CH4

(M + H)+(exp.) + CH4

(M + H - CH4)+=PhCH2+

(M + H - CH4)+=C7H7+

(M + H - C2H4)+=PhH2+

o-(M + H)+ + C2H4

m-(M + H)+ + C2H4

p-(M + H)+ + C2H4

i-(M + H)+ + C2H4

(M + H)+(exp.) + C2H4

o-(M + H)+ + C3H4

m-(M + H)+ + C3H4

p-(M + H)+ + C3H4

i-(M + H)+ + C3H4

(M + H)+(exp.) + C3H4

o-(M + C3H5)+

ΔH0

Products

Reactionsb)

8.07

9.39

10.61

9.89

9.87

9.34

9.17

9.29

9.11

9.60

8.69

9.17

9.29

9.11

9.60

8.69

10.61

10.73

10.54

11.04

10.13

9.29

9.43

9.24

9.82

9.92

9.95

9.80

9.63

9.53

9.01

7.67

7.80

7.59

8.04

7.08

7.78

7.26

8.62

8.98

9.11

8.91

9.35

8.39

10.42

10.55

10.34

10.79

9.83

9.09

-2.16

-0.82

-0.05

-0.77

-0.79

-1.32

-0.70

-0.58

-0.76

-0.27

-1.18

-0.70

-0.58

-0.76

-0.27

-1.18

0.29

0.41

0.22

0.72

-0.19

-1.03

-0.89

-1.08

-0.50

-0.40

-0.37

-0.52

-0.69

-0.79

-1.31

-2.00

-1.87

-2.08

-1.63

-2.59

-1.89

-2.41

-1.05

-0.67

-0.54

-0.74

-0.30

-1.26

0.32

0.45

0.24

0.69

-0.27

-1.01

Chemical

structurec)

5a

5b

5c

5d

5a

5b

5c

5d

5a

5b

5c

5d

6a

6b

6c

6d

7a

7b

7c

10

11a

11b

11c

11d

11

12

13

14

11a

11b

11c

11d

11

11a

11b

11c

11d

11

15a

Ion-molecule reactions of RH+ with aromatic hydrocarbons

10

Table A1. Continued.

m-(M + C3H5)+

p-(M + C3H5)+

i-(M + C3H5)+

o-C2H5C6H4CH2+ + C2H4

m-C2H5C6H4CH2+ + C2H4

p-C2H5C6H4CH2+ + C2H4

CH5+ + PhC2H3

10.90

C2H5+ + PhC2H3

10.88

C3H5+ + PhC2H3

11.33

CH5+ + PhC2H

12.53

C7H6C2H5+ + C2H4

PhCHCH3+ + C3H6

C7H6CH3+ + C3H6

PhCHCH3+

C7H6CH3+

PhCH2CH2+

o-(M + H)+ + CH4

m-(M + H)+ + CH4

p-(M + H)+ + CH4

i-(M + H)+ + CH4

(M + H)+(exp.) + CH4

PhCHCH3+ + C2H4

C7H6CH3+ + C2H4

PhCH2CH2+ + C2H4

o-(M + H)+ + C2H4

m-(M + H)+ + C2H4

p-(M + H)+ + C2H4

i-(M + H)+ + C2H4

(M + H)+(exp.) + C2H4

PhCHCH2C2H5+

PhCH(C2H5)CH2+

o-(M + C2H5)+

m-(M + C2H5)+

p-(M + C2H5)+

i-(M + C2H5)+

PhCH2+ + C3H6

C7H7+ + C3H6

PhCHCH3+ + C3H4

C7H6CH3+ + C3H4

PhCH2CH2+ + C3H4

o-(M + H)+ + C3H4

m-(M + H)+ + C3H4

p-(M + H)+ + C3H4

i-(M + H)+ + C3H4

(M + H)+(exp.) + C3H4

PhCHCH2C3H5+

PhCH(C3H5)CH2+

o-(M + C3H5)+

m-(M + C3H5)+

p-(M + C3H5)+

i-(M + C3H5)+

o-C2H3C6H4CH2+ + C2H4

m-C2H3C6H4CH2+ + C2H4

p-C2H3C6H4CH2+ + C2H4

C7H6C2H3+ + C2H4

PhCH2+ + C4H6

C7H7+ + C4H6

PhCHCH+ + CH4

PhCCH2+ + CH4

9.22

9.05

9.56

9.75

9.78

9.61

9.49

9.41

9.29

8.43

8.31

9.82

8.81

9.06

8.76

9.39

8.03

9.74

9.63

11.13

10.12

10.38

10.08

10.70

9.34

8.67

8.38

9.19

9.43

9.13

9.88

9.53

9.01

11.18

11.06

12.57

11.55

11.81

11.51

12.14

10.78

9.78

9.43

10.28

10.52

10.22

10.95

10.87

11.04

10.80

10.66

11.01

10.49

11.62

10.21

-0.88

-1.05

-0.54

-0.35

-0.32

-0.49

-0.61

-0.69

-0.81

-2.47

-2.59

-1.08

-2.09

-1.84

-2.14

-1.51

-2.87

-1.14

-1.25

0.25

-0.76

-0.50

-0.80

-0.18

-1.54

-2.21

-2.50

-1.69

-1.45

-1.75

-1.00

-1.35

-1.87

-0.15

-0.27

1.24

0.22

0.48

0.18

0.81

-0.55

-1.55

-1.90

-1.05

-0.81

-1.11

-0.38

-0.46

-0.29

-0.53

-0.67

-0.32

-0.84

-0.91

-2.32

15b

15c

15d

16a

16b

16c

17

18

19

20

21

22

23a

23b

23c

23d

23

20

21

22

23a

23b

23c

23d

23

24

25

26a

26b

26c

26d

27

28

20

21

22

23a

23b

23c

23d

23

29

30

31a

31b

31c

31d

32a

32b

32c

33

27

28

34

35

令和 2 年度

九州大学大学院総合理工学報告

第 41 巻

第2号

11

Table A1. Continued.

o-(M + H)+ + CH4

m-(M + H)+ + CH4

p-(M + H)+ + CH4

i-(M + H)+ + CH4

10.45

-2.08

36a

10.65

-1.88

36b

10.42

-2.11

36c

11.01

-1.52

36d

(M + H)+(exp.) + CH4

9.59

-2.94

36

C2H5 + PhC2H

12.51

PhCHCH+ + C2H4

12.94

0.43

34

PhCCH2++ C2H4

11.52

-0.99

35

o-(M + H)+ + C2H4

11.77

-0.74

36a

m-(M + H)+ + C2H4

11.96

-0.55

36b

p-(M + H)+ + C2H4

11.73

-0.78

36c

i-(M + H)+ + C2H4

12.32

-0.19

36d

(M + H)+(exp.) + C2H4

10.91

-1.60

36

PhCCHC2H5+

10.34

-2.17

37

PhC(C2H5)CH+

11.84

-0.67

38

o-(M + C2H5)+

10.86

-1.65

39a

m-(M + C2H5)+

11.02

-1.49

39b

p-(M + C2H5)+

10.78

-1.73

39c

i-(M + C2H5)+

11.44

-1.07

39d

PhCH2+ + C3H4

11.30

-1.21

40

C7H7+ + C2H4

10.78

-1.73

41

C3H5+ + PhC2H

12.97

o-(M + H)+ + C3H4

13.20

0.23

m-(M + H)+ + C3H4

13.40

0.43

p-(M + H)+ + C3H4

13.17

0.20

i-(M + H)+ + C3H4

13.76

0.79

(M + H)+(exp.) + C3H4

12.34

-0.63

PhCHCH+ + C3H4

14.37

1.40

34

PhCCH2+ + C3H4

12.96

-0.01

35

PhCCHC3H5+

11.44

-1.53

42

PhC(C3H5)CH+

12.87

-0.10

43

o-(M + C3H5)+

11.95

-1.02

44a

m-(M + C3H5)+

12.11

-0.86

44b

p-(M + C3H5)+

11.87

-1.10

44c

i-(M + C3H5)+

12.51

-0.46

44d

naphthalene+ + CH3

11.21

-1.76

45

o-C2HC6H4CH2+ + C2H4

12.50

-0.47

46a

m-C2HC6H4CH2+ + C2H4

12.62

-0.35

46b

p-C2HC6H4CH2+ + C2H4

12.44

-0.53

46c

C7H6C2H+

12.26

-0.71

47

PhCH2+ + CH2CCCH2

12.92

-0.05

40

C7H7+ + CH2CCCH2

12.40

-0.57

41

PhCH2+ + CH2CHCCH

12.49

-0.48

40

C7H7+ + CH2CHCCH

11.97

-1.00

41

a) The symbols o-, m-, p-, and i- represent ortho-, meta-, para-, and ipso-adduct ions, respectively.

Thermochemical data calculated using reliable experimental values for ions in Ref. 11 are

shown by exp., and the other values for ions are calculated using a PM3 method. b)

ΔH0(Reaction) = ΣΔH0(Product) – ΣΔH0(Reactant). (c) Chemical structures in Scheme 15.

...