suppmat1120. 27KB Jun 05 2011 09:30:55 PM

[image:1.612.74.539.160.679.2]

Table A. The difference between the infrared OH-stretching frequencies for the non-bonded and bonded O-H in various diols, calculated at the MPW1PW91/6-311+G(2d,p) level. Frequencies have not been scaled (see text).

DIOL O-HD...OA-H

distance Å

Non-bonded OH-stretch

(cm-1₎

Bonded H_D OH-stretch

(cm-1₎

red-shift

(cm-1₎

12EG(B) 2.338 3915 3857 58

12EG(D) 2.328 3881 3839 42

12PG(A) 2.244 3912 3843 69

12PG(B) 2.295 3916 3841 75

12PG(C) 2.273 3900 3849 52

12PG(D) 2.319 3896 3850 46

12PG(M) 2.248 3885 3828 57

12PG(N) 2.288 3895 3829 65

12PG(O) 2.251 3859 3829 30

12PG(P) 2.309 3880 3834 46

23BD(E) 2.263 3903 3835 68

23BD(F) 2.151 3904 3840 64

23BD(B) 2.248 3898 3843 55

23BD(X) 2.244 3906 3838 68

12BD(D) 2.306 3896 3852 44

12PD(D) 2.310 3896 3852 44

12HD(D) 2.309 3895 3852 43

Average (1,2) 2.278 3896 3842 54

± 0.046 14 9 12

DIOL O-H_D...O_A-H distance Å

Non-bonded OH-stretch

(cm-1₎

Bonded H_D OH-stretch

(cm-1₎

red-shift

(cm-1₎

2M13PG(A) 2.009 3904 3806 98

2M13PG(B) 1.976 3901 3804 97

13BD(A) 1.970 3904 3796 108

13BD(B) 2.014 3858 3790 68

24PD-meso 1.950 3888 3789 99

24PD-dl(A) 1.985 3887 3797 90

24PD-dl(B) 1.949 3887 3790 97

Average (1,3) 1.984 3892 3798 94

± 0.025 16 9 12

14BD(A) 1.849 3890 3707 183

25HD-dl(A) 1.821 3877 3692 185

25HD-meso(A) 1.859 3877 3702 175

Average (1,4) 1.843 3881 3700 181

± 0.020 7 8 5

15PD(A) 1.903 3906 3754 152

16HD(A) 1.982 3890 3725 164

Complexes TIP3 1:1

12EG(B)s _{1.890 3901 3693 208}

DIOL O-H_D...O_A-H distance Å

Non-bonded OH-stretch

(cm-1₎

Bonded H_D OH-stretch

(cm-1₎

red-shift

(cm-1₎

12EG(C)s _{2.051 3901 3825 76}

12EG(C)s _{2.051 3900 3810 91}

Cooperative B/D 1.876 3889 3664 225

[image:4.612.76.540.163.679.2]

Table B. The difference between the 1H nuclear shielding tensors (ppm downfield shift) for the non-bonded and bonded O-H protons in various diols, calculated at the

MPW1PW91/6-311+G(2d,p) level. Non-bonded H2O gave a value of 31.71 ppm.

DIOL O-HD...OA-H

distance Å

Non-bonded shielding tensor

(ppm)

Bonded H_D shielding tensor

(ppm)

) ppm downfield

shift

12EG(B) 2.338 31.72 30.35 1.37

12EG(D) 2.328 32.48 30.22 2.26

12PG(A) 2.244 31.65 29.66 2.00

12PG(B) 2.295 31.87 30.23 1.64

12PG(C) 2.273 31.52 30.36 1.16

12PG(D) 2.319 31.96 30.80 1.15

12PG(M) 2.248 32.19 29.56 2.63

12PG(N) 2.288 31.89 30.11 1.78

12PG(O) 2.251 32.80 30.19 2.61

12PG(P) 2.309 32.07 30.64 1.42

23BD(E) 2.263 32.07 30.74 1.33

23BD(F) 2.151 31.57 29.44 2.13

23BD(B) 2.248 31.83 30.22 1.61

23BD(X) 2.244 31.74 30.18 1.56

12BD(D) 2.306 30.98 30.78 0.19

12PD(D) 2.310 31.04 30.77 0.26

12HD(D) 2.309 31.02 30.77 0.24

DIOL O-H_D...O_A-H distance Å

Non-bonded shielding tensor

(ppm)

Bonded H_D shielding tensor

(ppm)

) ppm downfield

shift

2M13PG(A) 2.009 31.78 29.92 1.87

2M13PG(B) 1.976 31.64 29.12 2.52

13BD(A) 1.970 31.65 28.72 2.93

13BD(B) 2.014 32.25 28.95 3.30

24PD-meso 1.950 31.50 28.47 3.03

24PD-dl(A) 1.985 31.64 29.14 2.51

24PD-dl(B) 1.949 31.73 28.71 3.02

Average (1,3) 1.984 31.73 29.07 2.67

± 0.025 0.22 0.47 0.46

14BD(A) 1.849 31.33 28.00 3.33

25HD-dl(A) 1.821 31.36 27.28 4.08

25HD-meso(A) 1.859 31.40 28.19 3.21

Average (1,4) 1.843 31.36 27.82 3.54

± 0.020 0.04 0.48 0.47

15PD(A) 1.903 31.51 28.61 2.90

16HD(A) 1.982 31.52 28.75 2.77

Complexes TIP3 1:1

12EG(B) 1.890 31.37 27.24 4.13

H₂O 1.853 31.49 27.35 4.15

12EG(D) 1.890 31.75 27.17 4.57

DIOL O-H_D...O_A-H distance Å

Non-bonded shielding tensor

(ppm)

Bonded H_D shielding tensor

(ppm)

) ppm downfield

shift

12PG tGga 1.880 31.34 26.86 4.48

H₂O 1.846 31.47 27.36 4.10

12PG tGgb 1.880 31.27 27.21 4.06

H₂O 1.840 31.49 27.31 4.17

23BD-dl-tGg 1.910 31.70 28.15 3.55

H₂O 1.848 31.60 27.28 4.33

23BD-meso 1.887 31.57 27.47 4.10

H₂O 1.830 31.52 27.19 4.33

Average (1:1) 1.869 31.50 27.32 4.17

[image:7.612.75.539.148.703.2]

Table C. The difference in the O-H bond length for the non-bonded and bonded O-H in various diols, calculated at the MPW1PW91/6-311+G(2d,p) level.

DIOL O-HD...OA-H

distance Å

Non-bonded OA-H

Bonded O-HD Difference

Å x 103

12EG(B) 2.338 0.9581 0.9621 4.0

12EG(D) 2.328 0.9601 0.9630 2.9

12PG(A) 2.244 0.9580 0.9629 4.9

12PG(B) 2.295 0.9578 0.9630 5.2

12PG(C) 2.273 0.9588 0.9625 3.7

12PG(D) 2.319 0.9591 0.9624 3.3

12PG(M) 2.248 0.9600 0.9637 3.7

12PG(N) 2.288 0.9593 0.9638 4.5

12PG(O) 2.251 0.9617 0.9637 2.0

12PG(P) 2.309 0.9603 0.9634 3.1

23BD(E) 2.263 0.9588 0.9635 4.7

23BD(F) 2.151 0.9588 0.9632 4.4

23BD(B) 2.248 0.9591 0.9631 4.0

23BD(X) 2.244 0.9586 0.9633 4.7

12BD(D) 2.306 0.9590 0.9624 3.4

12PD(D) 2.310 0.9590 0.9624 3.4

12HD(D) 2.309 0.9590 0.9624 3.4

Average (1,2) 2.278 0.9591 0.9630 3.8

± 0.046 0.0010 0.0005 0.4

13PG 2.015 0.9588 0.9640 5.2

2M13PG(A) 2.009 0.9588 0.9643 5.5

DIOL O-H_D...O_A-H distance Å

Non-bonded OA-H

Bonded O-H_D Difference

Å x 103

13BD(A) 1.970 0.9610 0.9670 6.0

13BD(B) 2.014 0.9618 0.9651 3.3

24PD-meso 1.950 0.9597 0.9651 5.4

24PD-dl(A) 1.985 0.9596 0.9647 5.1

24PD-dl(B) 1.949 0.9597 0.9649 5.2

Average (1,3) 1.984 0.9598 0.9649 5.1

± 0.025 0.0011 0.0009 0.6

14BD(A) 1.849 0.9596 0.9684 8.8

25HD-dl(A) 1.821 0.9605 0.9691 8.6

25HD-meso(A) 1.859 0.9605 0.9689 8.4

Average (1,4) 1.843 0.9602 0.9688 8.6

± 0.020 0.0005 0.0004 0.2

15PD(A) 1.903 0.9587 0.9665 7.8

16HD(A) 1.982 0.9597 0.9677 8.0

Complexes TIP3 1:1

12EG(B) 1.890 0.9590 0.9704 11.4

12EG(B)h2o _{1.853 0.9587 0.9722 13.5}

12EG(D) 1.890 0.9607 0.9712 10.5

12EG(D)h2o _{1.870 0.9590 0.9725 13.5}

DIOL O-H_D...O_A-H distance Å

Non-bonded OA-H

Bonded O-H_D Difference

Å x 103

Cooperative B/D 1.876 0.9594 0.9716 12.2