suppmat135.doc 89KB Jun 05 2011 09:30:52 PM

SUPPLEMENTARY MATERIAL
ROLE OF THE ANOMERIC EFFECT IN METHANEDIAMINES IN GAS PHASE AND AQUEOUS SOLUTION
Luis Carballeira* and Ignacio Pérez-Juste
Departamento de Química Física. Facultad de Ciencias. Universidad de Vigo. Vigo. SPAIN.
e-mail: [email protected]

TABLE I. Relative energies (kcal/mol) at various computational levels for the stable conformers of the compounds of Scheme 1.
Methylenediamine
HF/4-31G//HF/4-31G

ref.
9a
ref.
ref.
ref.
9h
ref.
9h
ref.
ref.
ref.

9g

HF/4-21G//HF/4-21G
HF/3-21G//HF/3-21G
HF/6-31G/HF//6-31G
HF/6-31G*/HF//6-31G*
HF/6-31G*/HF//6-31G*
MP3/6-31G*//MP3/6-31G*
HF/6-31G**//HF/6-31G** b

a

9c
9f

9f
9f

N-Methylmethylenediamine
HF/3-21G//HF/3-21G


ref. 9f

1,1-Ethylenediamine
HF/4-31G//HF/4-31G

ref.
9b

N,N-Dimethylmethylenediamine
HF/3-21G//HF/3-21G
N,N,N’,N’-Tetramethylmethylenediamine
HF/3-21G//HF/3-21G
HF/6-31G//HF/6-31G
HF/6-31G*//HF/6-31G*

ref. 9f
c

ref. 9f

ref.
9h
ref.
9h

1TT

1TG

1TG’

0.60

0.00

0.34

5.86

0.00

0.00
0.00

1.58
1.63
1.07

2.38
2.71
1.35

8.08
8.26
ns

0.00

0.41

0.71


ns

0.00
0.00
0.00

0.43
0.55
0.64

0.71
1.13
0.82

5.20
5.70
nf

2TT


2TG

2TG’

2GT

2GG

2GG’

2G’T

2G’G

2G’G’

0.00

1.50


nf

1.69

2.48

nf

1.23

nf

2.27

3TT

3TG

3TG’


3GT

3GG

3GG’

3G’T

3G’G

3G’G’

5.13

0.00

0.75

0.71


6.81

4TT

4TG

4TG’

4GT

4GG

4GG’

0.00

1.27

nf


2.14

11TT

11TG

11GT

11GG

11GG’

ns
1.83

ns
2.13

0.00

0.00

ns
ns

4.82

3.66

0.00

ns

11TG’

1GT

1GG

Partial geometrical optimization
Constrained HNCN dihedral angles.
c
The ED spectrum was assigned to conformer 11GG (ref. 8).
nf: Structure not characterized as minimum or transition state at this computational level.
ns: Structure not studied at this computational level.
a
b

1GG’

1G’T

1G’G

1G’G’

0.91
4G’T

4G’G

4G’G’

nf
11G’T

11G’G

11G’G’

TABLE II. Selected HF/6-31G** geometrical parameters (bond lengths in Angstroms and bond angles in degrees) for the
stable conformers of the compounds of Scheme 1.
1

1TT

1TG

1TG’

1GT

1GG

1GG’

C2-N1
N3-C2
N3-C2-N1
H4-N1-C2
H5-N1-C2
H8-N3-C2
H9-N3-C2
N3-C2-N1-H4
N3-C2-N1-H5
H8-N3-C2-N1
H9-N3-C2-N1

1.4486
1.4487
118.60
111.55
111.55
111.53
111.54
-60.32
60.22
-60.28
60.23

1.4399
1.4554
113.37
109.70
111.12
111.14
111.14
-50.27
68.27
169.14
-71.37

2

2TT

2TG

2TG’

2GT

2GG

N3-C2
N3-C2-N1
C4-N1-C2
N3-C2-N1-C4
N3-C2-N1-H5
H8-N3-C2-N1
H9-N3-C2-N1

1.4468
1.4492
118.95
115.90
-61.77
65.28
-58.36
63.29

1.4374
1.4566
114.19
115.32
-58.78
67.37
165.44
-74.78

1.4385
1.4567
113.91
115.14
-67.69
56.00
77.94
-162.41

1.4517
1.4387
113.64
113.80
176.25
-60.39
-51.17
68.22

1.4408
1.4444
108.24
114.29
-178.38
-53.81
175.63
-63.97

3

3TT

3TG

3TG’

3GT

3GG

3GG’

C2-N1
N3-C2
N3-C2-N1
C6-C2-N1
C6-C2-N3
N3-C2-N1-H4
N3-C2-N1-H5
H8-N3-C2-N1
H9-N3-C2-N1

1.4539
1.4538
116.90
109.12
109.13
-62.05
57.79
-57.92
61.93

1.4450
1.4597
111.56
109.68
108.98
-51.28
67.04
176.73
-64.10

1.4443
1.4596
111.80
109.18
114.01
-68.95
49.15
70.65
-170.31

1.4488
1.4486
106.41
114.54
109.15
178.12
-61.83
-176.52
-56.32

1.4514
1.4513
108.32
113.24
113.23
176.90
-64.55
65.92
-175.53

4

4TT

4TG

4TG’

4GT

4GG

4GG’

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C5-N1-C2
N3-C2-N1-C4
N3-C2-N1-C5
H8-N3-C2-N1
H9-N3-C2-N1

1.4497
1.4485
119.08
114.21
114.21
-65.74
65.72
-61.34
61.28

1.4400
1.4569
114.41
113.63
113.69
-62.74
67.34
158.35
-81.40

1.4553
1.4382
115.22
111.69
113.16
165.62
-67.70
-48.97
72.11

1.4443
1.4451
109.98
112.23
112.90
166.65
-65.90
174.30
-65.20

1G’T

1.4444
1.4448
107.83
111.48
110.06
111.45
110.00
177.98
-61.45
178.15
-61.38

1G’G

1G’G’

1.4479
1.4480
109.85
110.92
110.41
110.39
110.90
67.30
-174.19
175.35
-66.17
2GG’

2G’T

2G’G

1.4521
1.4405
114.52
115.03
74.91
-160.60
-70.63
49.16
3G’T

2G’G’
1.4419
1.4458
109.26
114.76
71.25
-163.66
63.23
-176.06

3G’G

3G’G’

1.4517
1.4517
108.14
109.28
109.28
60.46
178.88
-178.92
-60.50
4G’T

4G’G

4G’G’

5

5TT

5TG

5TG’

5GT

5GG

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C6-C2-N1
C6-C2-N3
N3-C2-N1-C4
N3-C2-N1-H5
H8-N3-C2-N1
H9-N3-C2-N1

1.4571
1.4536
117.24
117.70
111.10
108.89
-58.27
67.79
-53.94
67.22

1.4466
1.4602
112.32
117.38
111.55
108.97
-55.51
70.53
175.33
-65.23

1.4481
1.4614
112.41
117.11
111.23
113.69
-63.41
59.28
78.92
-162.19

1.4575
1.4451
111.64
116.28
114.50
108.78
164.66
-68.94
-47.91
70.20

1.4468
1.4491
106.17
116.68
115.22
108.73
172.47
-59.82
-177.16
-56.78

6

6TT

6TG

6TG’

6GT

6GG

6GG’

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C8-N3-C2
N3-C2-N1-C4
N3-C2-N1-H5
C8-N3-C2-N1
H9-N3-C2-N1

1.4471
1.4472
119.12
115.86
115.87
-60.06
67.93
-60.03
67.96

1.4356
1.4531
114.36
115.57
113.65
-59.14
68.03
175.10
-61.66

1.4406
1.4406
108.59
114.26
114.26
179.84
-55.83
179.83
-55.84

1.4481
1.4429
110.86
113.90
115.58
-165.06
-39.65
96.65
-135.66

7

7TT

7TG

7TG’

7GG

7GG’

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C9-N3-C2
N3-C2-N1-C4
N3-C2-N1-H5
H8-N3-C2-N1
C9-N3-C2-N1

1.4463
1.4463
120.80
118.95
119.11
-70.38
61.28
-58.18
74.17

1.4376
1.4529
115.12
115.47
114.95
-56.91
70.54
159.56
-75.48

1.4370
1.4527
114.18
115.91
113.52
-69.57
55.77
63.92
-173.00

1.4422
1.4413
109.54
114.17
114.72
-179.59
-55.04
161.82
-73.06

1.4430
1.4430
110.69
113.38
113.38
178.79
-57.97
57.95
-178.81

8

8TT

8TG

8TG’

8GT

8GG

8GG’

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C5-N1-C2
C5-N1-C4
C6-C2-N1
C6-C2-N3
N3-C2-N1-C4
N3-C2-N1-C5
H8-N3-C2-N1
H9-N3-C2-N1

1.4615
1.4528
117.31
115.80
113.28
111.35
111.50
108.79
-61.04
69.37
-56.70
65.34

1.4506
1.4598
112.49
115.61
113.38
111.38
111.96
108.91
-57.96
72.40
171.38
-68.88

1.4513
1.4612
112.73
115.20
112.51
110.98
111.48
113.38
-60.94
67.62
82.37
-158.15

1.4646
1.4440
112.91
114.12
115.94
111.85
115.34
108.82
158.18
-69.65
-45.12
75.11

1.4534
1.4503
107.77
114.34
115.55
112.29
115.83
108.88
161.27
-66.08
-178.08
-57.89

9

9TT

9TG

9TG’

9GT

9GG

7GT

5GG’

9GG’

5G’T

5G’G

5G’G’

1.4569
1.4458
112.79
115.30
109.01
109.28
70.07
-165.79
-69.68
49.76

1.4501
1.4523
109.62
115.31
108.98
109.06
63.21
-173.70
169.37
-72.39

1.4463
1.4498
107.78
115.07
109.11
113.95
68.01
-167.31
63.15
-176.52

6G’T

6G’G

6G’G’
1.4427
1.4427
110.43
114.63
114.63
71.90
-162.68
71.88
-162.69

7G’T

7G’G

7G’G’

8G’T

8G’G

8G’G’

1.4676
1.4463
112.70
112.49
113.83
109.99
111.76
107.70
60.08
-173.95
-70.25
50.67

1.4635
1.4520
110.41
114.40
112.05
110.17
110.52
107.77
39.33
165.65
158.65
-81.89

1.4557
1.4523
107.56
112.17
114.54
110.21
112.22
112.13
61.69
-171.72
65.37
-174.95

9G’T

9G’G

9G’G’

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C5-N1-C2
C5-N1-C4
C8-N3-C2
N3-C2-N1-C4
N3-C2-N1-C5
C8-N3-C2-N1
H9-N3-C2-N1

1.4492
1.4455
120.73
114.79
117.56
113.29
118.70
-58.45
78.62
-67.37
64.66

10

10TT

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C6-C2-N1
C6-C2-N3
C9-N3-C2
N3-C2-N1-C4
N3-C2-N1-H5
H8-N3-C2-N1
C9-N3-C2-N1

1.4578
1.4564
117.76
119.54
110.77
111.35
121.06
-55.84
72.02
-46.15
85.84

11

11TT

C2-N1
N3-C2
N3-C2-N1
C4-N1-C2
C5-N1-C2
C5-N1-C4
C8-N3-C2
C9-N3-C2
C9-N3-C8
N3-C2-N1-C4
N3-C2-N1-C5
C8-N3-C2-N1
C9-N3-C2-N1

1.4477
1.4477
122.32
117.63
117.63
113.34
117.63
117.63
113.34
-70.56
70.58
-70.57
70.58

1.4379
1.4533
114.66
114.00
114.54
112.62
113.46
-62.20
69.57
172.02
-64.84
10TG
1.4475
1.4564
113.31
117.35
111.14
109.05
115.21
-52.86
74.22
165.53
-69.61
11TG
1.4364
1.4565
116.82
115.25
119.29
114.09
111.54
113.97
111.33
-53.15
88.28
160.77
-72.11

1.4561
1.4349
115.72
111.75
113.00
111.59
115.72
165.73
-67.42
-56.33
72.53
10TG’

10GT

1.4491
1.4592
112.37
117.29
110.93
113.96
115.78
-64.30
58.40
77.01
-157.21
11TG’

1.4436
1.4418
110.18
112.38
112.80
111.77
114.02
164.97
-67.58
179.41
-56.33
10GG

1.4539
1.4393
114.71
114.11
111.59
111.61
119.00
66.42
-165.93
-99.83
33.68

1.4471
1.4441
112.71
113.38
110.87
111.74
113.35
58.89
-174.47
161.47
-75.92

1.4455
1.4415
111.04
112.76
112.26
111.95
114.57
66.24
-166.20
72.97
-161.60

10GG’

10G’T

10G’G

10G’G’

11GG’

11G’T

11G’G

11G’G’

1.4475
1.4471
107.59
116.82
114.55
108.72
115.15
169.87
-61.76
166.44
-68.71
11GT

11GG
1.4444
1.4444
111.59
112.24
112.63
111.96
112.24
112.63
111.96
165.35
-67.19
165.34
-67.19

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