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: uviqplco@cesga.es

TABLE I. Relative energies (kcal/mol) at various computational levels for the stable conformers of the compounds of Scheme 1.

Methylenediamine 1TT 1TG 1TG’ 1GT 1GG 1GG’ 1G’T 1G’G 1G’G’

HF/4-31G//HF/4-31G ref.

9a 0.60 0.00 0.34 5.86

HF/4-21G//HF/4-21G ref. 9c 0.00 1.58 2.38 8.08

HF/3-21G//HF/3-21G ref. 9f 0.00 1.63 2.71 8.26

HF/6-31G/HF//6-31G ref.

9h 0.00 1.07 1.35 ns

HF/6-31G*/HF//6-31G* ref.

9h 0.00 0.41 0.71 ns

HF/6-31G*/HF//6-31G* ref. 9f 0.00 0.43 0.71 5.20

MP3/6-31G*//MP3/6-31G* a _{ref. 9f 0.00 0.55 1.13 5.70}

HF/6-31G**//HF/6-31G** b _ref.

9g 0.00 0.64 0.82 nf

N-Methylmethylenediamine 2TT 2TG 2TG’ 2GT 2GG 2GG’ 2G’T 2G’G 2G’G’

HF/3-21G//HF/3-21G ref. 9f 0.00 1.50 nf 1.69 2.48 nf 1.23 nf 2.27

1,1-Ethylenediamine 3TT 3TG 3TG’ 3GT 3GG 3GG’ 3G’T 3G’G 3G’G’

HF/4-31G//HF/4-31G ref.

9b 5.13 0.00 0.75 0.71 6.81 0.91

N,N-Dimethylmethylenediamine 4TT 4TG 4TG’ 4GT 4GG 4GG’ 4G’T 4G’G 4G’G’

HF/3-21G//HF/3-21G ref. 9f 0.00 1.27 nf 2.14 nf

N,N,N’,N’-Tetramethylmethylenediamine c _{11TT 11TG 11TG’ 11GT 11GG 11GG’ 11G’T 11G’G 11G’G’}

HF/3-21G//HF/3-21G ref. 9f ns ns 0.00 ns

HF/6-31G//HF/6-31G ref.

9h 1.83 2.13 0.00 ns

HF/6-31G*//HF/6-31G* ref.

9h 4.82 3.66 0.00 ns

a _{Partial geometrical optimization} b _{Constrained HNCN dihedral angles.}

c _{The ED spectrum was assigned to conformer 11GG (ref. 8).}

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’ 1G’T 1G’G 1G’G’

C2-N1 1.4486 1.4399 1.4444 1.4479

N3-C2 1.4487 1.4554 1.4448 1.4480

N3-C2-N1 118.60 113.37 107.83 109.85

H4-N1-C2 111.55 109.70 111.48 110.92

H5-N1-C2 111.55 111.12 110.06 110.41

H8-N3-C2 111.53 111.14 111.45 110.39

H9-N3-C2 111.54 111.14 110.00 110.90

N3-C2-N1-H4 -60.32 -50.27 177.98 67.30

N3-C2-N1-H5 60.22 68.27 -61.45 -174.19

H8-N3-C2-N1 -60.28 169.14 178.15 175.35

H9-N3-C2-N1 60.23 -71.37 -61.38 -66.17

2 2TT 2TG 2TG’ 2GT 2GG 2GG’ 2G’T 2G’G 2G’G’

1.4468 1.4374 1.4385 1.4517 1.4408 1.4521 1.4419

N3-C2 1.4492 1.4566 1.4567 1.4387 1.4444 1.4405 1.4458

N3-C2-N1 118.95 114.19 113.91 113.64 108.24 114.52 109.26

C4-N1-C2 115.90 115.32 115.14 113.80 114.29 115.03 114.76

N3-C2-N1-C4 -61.77 -58.78 -67.69 176.25 -178.38 74.91 71.25

N3-C2-N1-H5 65.28 67.37 56.00 -60.39 -53.81 -160.60 -163.66

H8-N3-C2-N1 -58.36 165.44 77.94 -51.17 175.63 -70.63 63.23

H9-N3-C2-N1 63.29 -74.78 -162.41 68.22 -63.97 49.16 -176.06

3 3TT 3TG 3TG’ 3GT 3GG 3GG’ 3G’T 3G’G 3G’G’

C2-N1 1.4539 1.4450 1.4443 1.4488 1.4514 1.4517

N3-C2 1.4538 1.4597 1.4596 1.4486 1.4513 1.4517

N3-C2-N1 116.90 111.56 111.80 106.41 108.32 108.14

C6-C2-N1 109.12 109.68 109.18 114.54 113.24 109.28

C6-C2-N3 109.13 108.98 114.01 109.15 113.23 109.28

N3-C2-N1-H4 -62.05 -51.28 -68.95 178.12 176.90 60.46

N3-C2-N1-H5 57.79 67.04 49.15 -61.83 -64.55 178.88

H8-N3-C2-N1 -57.92 176.73 70.65 -176.52 65.92 -178.92

H9-N3-C2-N1 61.93 -64.10 -170.31 -56.32 -175.53 -60.50

4 4TT 4TG 4TG’ 4GT 4GG 4GG’ 4G’T 4G’G 4G’G’

C2-N1 1.4497 1.4400 1.4553 1.4443

N3-C2 1.4485 1.4569 1.4382 1.4451

N3-C2-N1 119.08 114.41 115.22 109.98

C4-N1-C2 114.21 113.63 111.69 112.23

C5-N1-C2 114.21 113.69 113.16 112.90

N3-C2-N1-C4 -65.74 -62.74 165.62 166.65

N3-C2-N1-C5 65.72 67.34 -67.70 -65.90

H8-N3-C2-N1 -61.34 158.35 -48.97 174.30

5 5TT 5TG 5TG’ 5GT 5GG 5GG’ 5G’T 5G’G 5G’G’

C2-N1 1.4571 1.4466 1.4481 1.4575 1.4468 1.4569 1.4501 1.4463

N3-C2 1.4536 1.4602 1.4614 1.4451 1.4491 1.4458 1.4523 1.4498

N3-C2-N1 117.24 112.32 112.41 111.64 106.17 112.79 109.62 107.78

C4-N1-C2 117.70 117.38 117.11 116.28 116.68 115.30 115.31 115.07

C6-C2-N1 111.10 111.55 111.23 114.50 115.22 109.01 108.98 109.11

C6-C2-N3 108.89 108.97 113.69 108.78 108.73 109.28 109.06 113.95

N3-C2-N1-C4 -58.27 -55.51 -63.41 164.66 172.47 70.07 63.21 68.01

N3-C2-N1-H5 67.79 70.53 59.28 -68.94 -59.82 -165.79 -173.70 -167.31 H8-N3-C2-N1 -53.94 175.33 78.92 -47.91 -177.16 -69.68 169.37 63.15 H9-N3-C2-N1 67.22 -65.23 -162.19 70.20 -56.78 49.76 -72.39 -176.52

6 6TT 6TG 6TG’ 6GT 6GG 6GG’ 6G’T 6G’G 6G’G’

C2-N1 1.4471 1.4356 1.4406 1.4481 1.4427

N3-C2 1.4472 1.4531 1.4406 1.4429 1.4427

N3-C2-N1 119.12 114.36 108.59 110.86 110.43

C4-N1-C2 115.86 115.57 114.26 113.90 114.63

C8-N3-C2 115.87 113.65 114.26 115.58 114.63

N3-C2-N1-C4 -60.06 -59.14 179.84 -165.06 71.90

N3-C2-N1-H5 67.93 68.03 -55.83 -39.65 -162.68

C8-N3-C2-N1 -60.03 175.10 179.83 96.65 71.88

H9-N3-C2-N1 67.96 -61.66 -55.84 -135.66 -162.69

7 7TT 7TG 7TG’ 7GT 7GG 7GG’ 7G’T 7G’G 7G’G’

C2-N1 1.4463 1.4376 1.4370 1.4422 1.4430

N3-C2 1.4463 1.4529 1.4527 1.4413 1.4430

N3-C2-N1 120.80 115.12 114.18 109.54 110.69

C4-N1-C2 118.95 115.47 115.91 114.17 113.38

C9-N3-C2 119.11 114.95 113.52 114.72 113.38

N3-C2-N1-C4 -70.38 -56.91 -69.57 -179.59 178.79

N3-C2-N1-H5 61.28 70.54 55.77 -55.04 -57.97

H8-N3-C2-N1 -58.18 159.56 63.92 161.82 57.95

C9-N3-C2-N1 74.17 -75.48 -173.00 -73.06 -178.81

8 8TT 8TG 8TG’ 8GT 8GG 8GG’ 8G’T 8G’G 8G’G’

C2-N1 1.4615 1.4506 1.4513 1.4646 1.4534 1.4676 1.4635 1.4557

N3-C2 1.4528 1.4598 1.4612 1.4440 1.4503 1.4463 1.4520 1.4523

N3-C2-N1 117.31 112.49 112.73 112.91 107.77 112.70 110.41 107.56

C4-N1-C2 115.80 115.61 115.20 114.12 114.34 112.49 114.40 112.17

C5-N1-C2 113.28 113.38 112.51 115.94 115.55 113.83 112.05 114.54

C5-N1-C4 111.35 111.38 110.98 111.85 112.29 109.99 110.17 110.21

C6-C2-N1 111.50 111.96 111.48 115.34 115.83 111.76 110.52 112.22

C6-C2-N3 108.79 108.91 113.38 108.82 108.88 107.70 107.77 112.13

N3-C2-N1-C4 -61.04 -57.96 -60.94 158.18 161.27 60.08 39.33 61.69

N3-C2-N1-C5 69.37 72.40 67.62 -69.65 -66.08 -173.95 165.65 -171.72 H8-N3-C2-N1 -56.70 171.38 82.37 -45.12 -178.08 -70.25 158.65 65.37 H9-N3-C2-N1 65.34 -68.88 -158.15 75.11 -57.89 50.67 -81.89 -174.95

C2-N1 1.4492 1.4379 1.4561 1.4436 1.4539 1.4471 1.4455

N3-C2 1.4455 1.4533 1.4349 1.4418 1.4393 1.4441 1.4415

N3-C2-N1 120.73 114.66 115.72 110.18 114.71 112.71 111.04

C4-N1-C2 114.79 114.00 111.75 112.38 114.11 113.38 112.76

C5-N1-C2 117.56 114.54 113.00 112.80 111.59 110.87 112.26

C5-N1-C4 113.29 112.62 111.59 111.77 111.61 111.74 111.95

C8-N3-C2 118.70 113.46 115.72 114.02 119.00 113.35 114.57

N3-C2-N1-C4 -58.45 -62.20 165.73 164.97 66.42 58.89 66.24

N3-C2-N1-C5 78.62 69.57 -67.42 -67.58 -165.93 -174.47 -166.20

C8-N3-C2-N1 -67.37 172.02 -56.33 179.41 -99.83 161.47 72.97

H9-N3-C2-N1 64.66 -64.84 72.53 -56.33 33.68 -75.92 -161.60

10 10TT 10TG 10TG’ 10GT 10GG 10GG’ 10G’T 10G’G 10G’G’

C2-N1 1.4578 1.4475 1.4491 1.4475

N3-C2 1.4564 1.4564 1.4592 1.4471

N3-C2-N1 117.76 113.31 112.37 107.59

C4-N1-C2 119.54 117.35 117.29 116.82

C6-C2-N1 110.77 111.14 110.93 114.55

C6-C2-N3 111.35 109.05 113.96 108.72

C9-N3-C2 121.06 115.21 115.78 115.15

N3-C2-N1-C4 -55.84 -52.86 -64.30 169.87

N3-C2-N1-H5 72.02 74.22 58.40 -61.76

H8-N3-C2-N1 -46.15 165.53 77.01 166.44

C9-N3-C2-N1 85.84 -69.61 -157.21 -68.71

11 11TT 11TG 11TG’ 11GT 11GG 11GG’ 11G’T 11G’G 11G’G’

C2-N1 1.4477 1.4364 1.4444

N3-C2 1.4477 1.4565 1.4444

N3-C2-N1 122.32 116.82 111.59

C4-N1-C2 117.63 115.25 112.24

C5-N1-C2 117.63 119.29 112.63

C5-N1-C4 113.34 114.09 111.96

C8-N3-C2 117.63 111.54 112.24

C9-N3-C2 117.63 113.97 112.63

C9-N3-C8 113.34 111.33 111.96

N3-C2-N1-C4 -70.56 -53.15 165.35

N3-C2-N1-C5 70.58 88.28 -67.19

C8-N3-C2-N1 -70.57 160.77 165.34