suppmat1827. 36KB Jun 05 2011 09:30:45 PM

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SUPPLEMENTARY MATERIAL

(Tables 6-8, 10, 12, 14, 19, 20, 24, 25, 28, 29)

MOLECULAR MECHANICS STUDIES (MM4) OF SULFIDES AND MERCAPTANS

Norman L. Allinger and Yi Fan

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Table 6. Comparison of Calculated and Experimental Geometries of 1-Propanethiol

Bond Length ( Å ) and Bond Angles ( )

(ag, C1)

Parameter MM3(rg) MM4(rg) MW(rs)30

S-H 1.343 1.333 1.336

S-C 1.834 1.824 1.814

C-C(Me) 1.537 1.536 1.536

C-C(Methylene) 1.534 1.535 1.528

CSH 97.0 96.6 96.0

CCC 112.2 111.9 111.7

CCS 111.8 113.3 113.6

CCSH 62.2 64.2 61.7

CCCS 179.3 178.2 180.0

Moments of Inertia

rg(MM3) rz(MM4) MW30

Ia 21.8179/3.22% 21.0458/-0.44% 21.1388

Ib 216.0568/0.26% 215.9561/0.23% 215.4577

Ic 225.6166/0.45% 225.1830/0.27% 224.5783

(aa, Cs)

Parameter MM3 MM4 MW(rs)30

S-H 1.343 1.333 1.336

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(Table 6 continued)

Moments of Inertia

Ia 21.1514/-1.89% 21.0812/-0.53% 21.1940

Ib 216.8275/2.69% 211.8501/0.33% 211.1483

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Table 7. Comparison of Calculated and Experimental Geometries of 2-Propanethiola

Parameter MM3 MM4 MW(rz)31

S-H 1.343 1.333 1.345

S-C 1.841 1.827 1.849

C-C 1.537 1.535 1.520

CSH 97.4 96.4 96.5

CCC 110.7 110.9 113.6

CCS 110.2 111.1 111.2

CCSH 61.2 62.0 61.0

Moments of Inertia(Cs)

Ia 64.9556/1.45% 64.2363/0.29% 64.0515

Ib 115.0802/0.51% 114.2347/-0.13% 114.3780

Ic 159.9976/-0.02% 159.2697/-0.65% 160.3185

Moments of Inertia(C1)

Ia 64.5926/0.72% 64.3422/0.33% 64.1331

Ib 114.6337/2.63% 111.7507/0.05% 111.6954

Ic 162.0758/1.64% 158.8753/-0.36% 159.4571

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Table 8. Comparison of Calculated and Experimental Geometries of Diisopropyl Sulfide (I, C2)

Parameter MM3 MM4 MOCED(rg)a

S-C 1.832 1.830 1.829(3)

C1-C4 1.538 1.538 1.528(2)

C1-C5 1.537 1.535 1.532(2)

C-H 1.114 1.112 1.118(3)

CSC 100.9 102.0 102.9(17)

C4C1S2 110.5 112.5 112.0(7)

C5C1S2 109.0 106.0 106.5(7)

CCC 110.1 110.2 110.5(9)

CSCH 42.0 53.0 59(7)

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a _{This structure was investigated by the molecular orbital constrained electron}

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Table 10. Comparison of Calculated and Experimental Geometries of Thiacyclopentane(C2)

Parameter MM3(rg) MM4(rg) MM4(re) MP2/6-31G** ED(rg)36

C-C_ave 1.537 1.537 1.530 1.526 1.536(2)

C-S 1.840 1.838 1.830 1.830 1.839(2)

CSC 93.3 93.4 / 93.7 93.4(5)

SCC 106.6 106.9 / 106.3 106.1(4)

CCC 105.5 105.9 / 106.0 105.0(5)

C5S1C2C3 -14.2 -13.8 / -14.0 -14.8(5)

S1C2C3C4 39.0 37.8 / 38.3 40.5(12)

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Table 12. Comparison of Calculated and Experimental Geometries of Thiane (Cs)

Parameter MM3 MM4 MW39 _ED40

C-C 1.536 1.531 1.533 1.528(3)

C-S 1.813 1.814 1.832 1.811(4)

C-H 1.114 1.113 1.095 1.114(2)

CSC 97.5 97.4 99.2 97.6(8)

C2C3C4 112.7 112.7 107.9 112.3(4)

C3C4C5 112.6 112.9 109.2 113.6(8)

HCH 106.4 106.4 108.5 105.9(9)

CCS 111.3 112.8 114.1 112.7(2)

Moments of Inertia

Ia 127.673/0.87% 125.9488/-0.50% 126.575

Ib 168.229/1.08% 168.9888/0.51% 168.134

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Table 14. Dipole Moments(Debye)

Compound MM3 MM4 Exp. Ref.

Methanethiol 1.410 1.552 1.532 21

Ethanethiol(gauche) 1.410 1.561 1.61±0.05 41

Ethanethiol(trans) 1.410 1.557 1.560±0.032 42

Dimethyl Sulfide 1.570 1.559 1.50±0.01 26

Methylethylsulfide(trans) 1.549 1.560 1.554±0.004 43

1-Propanethiol(aa) 1.413 1.558 1.598±0.054 30

1-Propanethiol(ag) 1.410 1.561 1.683±0.010 30

2-Propanethiol(trans) 1.404 1.564 1.61±0.02 31

2-Propanethiol(gauche) 1.409 1.564 1.53±0.02 31

1-butanethiol 1.413 1.558 1.55a ₄₄

2-butanethiol 1.408 1.566 1.50a ₄₄

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Table 19. Vibrational Spectrum of trans-Methyl Ethyl Sulfide(Cs) (cm-1)

MP2/6-31G* MM3 MM4 Diff.(MM4 - ab initio) Assignment

2994 2987 2998 4 Asy. CH3 str.

1297 1376 1348 51 CH2 wagging

1248 1278 1250 2 CH2 twist

341 332 341 0 CCS bending

249 265 254 5 CH3 torsion

197 231 228 31 CSC bending

167 201 190 23 CH3 torsion

74 86 84 10 CSCC torsion

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Table 20. Vibrational Spectrum of Thiacyclopentane(C2) (cm-1)

MP2/6-31G**a _MM3 _MM4 _{Diff.(MM4 -}_{ab initio}₎ _Assignment

2965 2944 2964 -1 C-H str.

2964 2944 2964 0 C-H str.

2944 2937 2939 -5 C-H str.

2937 2936 2937 0 C-H str.

2898 2892 2909 11 C-H str.

2898 2889 2908 10 C-H str.

2883 2881 2888 5 C-H str.

2882 2873 2878 4 C-H str.

1484 1446 1506 22 CH2 bending

1472 1444 1499 27 CH2 bending

1461 1443 1469 8 CH2 bending

1458 1433 1448 -10 CH2 bending

1336 1393 1420 84 CH2 wagging

1313 1365 1374 61 CH2 wagging

1294 1335 1278 -16 CH2 wagging

1265 1291 1272 27 CH2 wagging

1220 1221 1209 -11 CH2 twist

1200 1218 1200 0 CH2 twist

1134 1163 1151 17 CH2 twist

1059 1142 1125 66 CH2 twist

1037 1022 1060 23 CH2 twist

1031 1016 1001 -30 CC str.

960 972 993 33 CC str.

885 830 904 19 ring def. (CCC)

882 906 888 6 ring def. (CSC, CC)

878 875 825 -53 CH2 rock

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a_{The wavenumbers for C-H stretching are scaled down to 92% of original values,}

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Table 24. Relative Stability of Methyl Ethyl Sulfide Conformers

anti-gauche Method Ref.

0.0 IR E 54

0.14±0.05 IR(Liquid) E 55

0.0 IR H 53

0.00 MP2/6-31G* E this work

0.12 MM4 G this work

-0.07 MM4 ∆E this work

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Table 25. Input for the Heat Calculations of Sulfides and Mercaptans

WT Hf(0) ENTHALPY SUMH Hatom POP TORS COMPOUND 10 -5.47 30.31 -317.18 445.71 0.00 -0.57 METHANETHIOL 10 -11.07 49.78 -617.93 721.59 0.10 0.00 ETHANETHIOL 10 -8.96 48.95 -634.36 721.59 0.00 0.00 DIMETHYLSULFIDE 10 -16.23 68.71 -918.58 997.47 0.31 0.57 1-PROPANETHIOL

7 -14.24 68.71 -935.11 997.47 0.11 0.57 2-THIABUTANE 9 -19.96 88.46 -1235.86 1273.35 0.29 1.14 3-THIAPENTANE 10 -18.21 68.56 -918.68 997.47 0.10 0.00 2-PROPANETHIOL

9 -21.63 88.14 -1235.86 1273.35 0.15 0.57 3-ME-2THIABUTANE 8 -45.15 169.59 -2438.86 2376.87 0.00 1.14 DI-T-BUTYLSULFIDE 7 -8.15 78.67 -1108.94 1169.17 0.00 0.57 THIACYCLOPENTANE 8 -15.18 95.69 -1409.12 1445.05 0.00 0.00 THIACYCLOHEXANE 8 -22.97 114.87 -1693.25 1720.93 0.16 0.00 CYCLOHEXANETHIOL 7 -24.43 106.55 -1536.41 1549.23 0.51 1.71 2-THIAHEXANE

9 -28.99 107.40 -1536.61 1549.23 0.04 0.57 3,3DIME-2THIABUTA 8 -23.26 88.54 -1220.59 1273.35 0.16 0.57 2ME1PROPANETHIOL 8 -26.20 87.29 -1219.43 1273.35 0.00 0.00 2ME2PROPANETHIOL 8 -30.38 107.70 -1520.08 1549.23 0.12 0.57 2ME2BUTANETHIOL 7 -28.01 107.86 -1536.61 1549.23 0.21 1.14 2ME3THIAPENTANE 5 -35.37 127.10 -1837.35 1825.11 0.16 1.14 2,2DIME3THIAPENTA 6 -33.91 127.32 -1837.35 1825.11 0.40 1.14 2,4DIME3THIAPENTA 9 -11.42 102.11 -1393.07 1445.05 0.14 0.57 CYCLOPENTANETHIOL 9 -16.34 97.56 -1409.69 1445.05 0.16 0.57 2-METHIACYCLOPENT 7 -2.32 51.62 -512.11 787.24 0.19 0.57 ETHANE12DITHIOL

COMPOUND C-S S-H SEC TER S-Me SCCS

METHANETHIOL 1 1 0 0 1 0

ETHANETHIOL 1 1 0 0 0 0

DIMETHYLSULFIDE 2 0 0 0 2 0

1-PROPANETHIOL 1 1 0 0 0 0

THIACYCLOPENTANE 2 0 0 0 0 0

THIACYCLOHEXANE 2 0 0 0 0 0

CYCLOHEXANETHIOL 1 1 1 0 0 0

2-THIAHEXANE 2 0 0 0 1 0

3,3DIME-2THIABUT 2 0 0 1 1 0

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2ME3THIAPENTANE 2 0 1 0 0 0

2,2DIME3THIAPENT 2 0 0 1 0 0

2,4DIME3THIAPENT 2 0 2 0 0 0

CYCLOPENTANETHIOL 1 1 1 0 0 0

2-METHIACYCLOPEN 2 0 1 0 0 0

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Table 28. Strainless Heats of Formation of Sulfides and Mercaptans

WT Hf(0)a _ENTHALPY _{SUMH Hatom POP TORS COMPOUND}

10 -4.63 0.00 -295.31 445.71 0.00 0.00 METHANETHIOL 10 -11.16 0.00 -576.84 721.59 0.00 0.00 ETHANETHIOL 10 -9.02 0.00 -590.63 721.59 0.00 0.00 DIMETHYLSULFIDE 10 -17.00 0.00 -858.57 997.47 0.00 0.00 1-PROPANETHIOL

7 -15.26 0.00 -872.16 997.47 0.00 0.00 2-THIABUTANE 10 -18.75 0.00 -858.38 997.47 0.00 0.00 2-PROPANETHIOL

8 -26.62 0.00 -1139.91 1273.35 0.00 0.00 2ME2PROPANETHIOL 8 -11.84 0.00 -1069.22 1339.00 0.00 0.00 25DITHIAHEXANE

COMPOUND C-S S-H SEC TER S-Me SCCS

METHANETHIOL 1 1 0 0 1 0

ETHANETHIOL 1 1 0 0 0 0

DIMETHYLSULFIDE 2 0 0 0 2 0

2-THIABUTANE 2 0 0 0 1 0

2ME2PROPANETHIOL 1 1 0 1 0 0

25DITHIAHEXANE 4 0 0 0 2 1

Best Values:

C-S = -70.7021 S-H = -85.1621 SEC = -1.9757 TER = -4.1957 S-ME = 0.7528 SCCS = -0.3171

WT Hfb _Hf(0)a _Hf-Hf(0) _COMPOUND