SCH-Br Summary of spectra vs T, (slides: 3-7 (“hot”); 10-11(“cold”))

16
Br ry of spectra vs T, (slides: 3-7 (“hot”); 10-11(“cold”)) vs. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C es 11) analysis for C3-C5 (slides: 12-14) s: ://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-160712.ppt : //notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp : //notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls //notendur.hi.is/agust/rannsoknir/SCH/July12/ibrcl-silacyclo-nmr.xlsx Si Br H Si Br H

description

SCH-Br Summary of spectra vs T, (slides: 3-7 (“hot”); 10-11(“cold”)) calc. vs. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C4) (slides 11) DNMR-analysis for C3-C5 (slides: 12-14) PPT´s: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-160712.ppt IGOR´s: - PowerPoint PPT Presentation

Transcript of SCH-Br Summary of spectra vs T, (slides: 3-7 (“hot”); 10-11(“cold”))

SCH-Br•Summary of spectra vs T, (slides: 3-7 (“hot”); 10-11(“cold”))•calc. vs. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C4)(slides 11)•DNMR-analysis for C3-C5 (slides: 12-14)

PPT´s: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-160712.ppt IGOR´s:https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp XLS´s : https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls https://notendur.hi.is/agust/rannsoknir/SCH/July12/ibrcl-silacyclo-nmr.xlsx

SiBr

H

Si

Br

H

nuts and txt-TNMR [K] z Tcorr [K] file names i: size/K

180 -0.31566825 167.889512SCH-Br-180-150712i b 64170 -0.50446504 158.645267 b 64160 -0.69326184 149.73963 b 64156 -0.76878056 146.240126 b 64152 -0.84429928 142.757617 b 64148 -0.919818 139.276588 b 64144 -0.99533672 135.77923 b 64140 -1.07085544 132.245325 b 64136 -1.14637416 128.652129 b 64132 -1.22189288 124.974252 b 64128 -1.2974116 121.183542 b 64124 -1.37293032 117.24897 b 64

high b 64

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

1600

1400

1200

1000

800

600

400

200

0

30 25 20 15

TNMR [K] Tcorr [K]

high

180 167.889512

170 158.645267

160 149.73963

156 146.240126

152 142.757617

148 139.276588

144 135.77923

140 132.245325

136 128.652129

132 124.974252

128 121.183542

124 117.24897

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp

C4 C3,C5 C2,C6

ppm

SCH-Br

1600

1400

1200

1000

800

600

400

200

0

17 16 15 14

TNMR [K] Tcorr [K]

high

180 167.889512

170 158.645267

160 149.73963

156 146.240126

152 142.757617

148 139.276588

144 135.77923

140 132.245325

136 128.652129

132 124.974252

128 121.183542

124 117.24897

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp

C2,C6

ppm

SCH-Br

1600

1400

1200

1000

800

600

400

200

0

27 26 25 24 23 22

TNMR [K] Tcorr [K]

high

180 167.889512

170 158.645267

160 149.73963

156 146.240126

152 142.757617

148 139.276588

144 135.77923

140 132.245325

136 128.652129

132 124.974252

128 121.183542

124 117.24897

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp

ppm

SCH-Br

C3,C5

eq. ax.

X

X

1600

1400

1200

1000

800

600

400

200

0

32 31 30 29

TNMR [K] Tcorr [K]

high

180 167.889512

170 158.645267

160 149.73963

156 146.240126

152 142.757617

148 139.276588

144 135.77923

140 132.245325

136 128.652129

132 124.974252

128 121.183542

124 117.24897

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp

ppm

SCH-Br

C4

600

500

400

300

200

100

0

30 25 20 15

132 124.974252

128 121.183542

124 117.24897

Calc,

ax.-eq = +0.34 -3.83 -2.14

C4 C3,C5 C2,C6

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp

https://notendur.hi.is/agust/rannsoknir/SCH/July12/ibrcl-silacyclo-nmr.xlsx

SCH-Br

ppm

Comments:

• Chemical shift calculations seem to overestimate abs(ax.-eq.) spacings for C2/C6 & C3/C5

•Not clear what is the case for C4

•Only possible to determne chemical shift for eq. ForC3,C5

•Further cooling needed to determine chemical shifts for eq. For C2,C6 and C4

New “colder” spectra added:

1500

1000

500

0

30 25 20 15

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp

ppm

TNMR [K] Tcorr [K]

high

180 167.889512

170 158.645267

160 149.73963

156 146.240126

152 142.757617

148 139.276588

144 135.77923

140 132.245325

136 128.652129

132 124.974252

128 121.183542

124 117.24897

C4 C3,C5 C2,C6

SCH-Br TNMR [K] Tcorr [K]

160 149.7396

150 141.018

140 132.2453

130 123.0949

124 117.249

120 113.1365

117 109.9132

600

400

200

0

-200

-400

30 25 20 15

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp , Layout:0, Gr:0

ppm

C4 C3,C5 C2,C6

SCH-Br TNMR [K] Tcorr [K]

130 123.0949

124 117.249

120 113.1365

117 109.9132

132 124.974252

128 121.183542

124 117.24897

eq eq

-400

-300

-200

-100

0

30 25 20 15https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp ppm

C4 C3,C5 C2,C6

SCH-Br

eq eq

ax.-eq = +0.34 -3.83 -2.14 -2.889 -1.284

https://notendur.hi.is/agust/rannsoknir/SCH/July12/ibrcl-silacyclo-nmr.xlsx

Calc.Exp.

TNMR [K] Tcorr [K]

124 117.249

120 113.1365

117 109.9132

22.89449 ppm25.78859 ppm

parameter value unit

R 8.315J K-1 mol-1<T> 128.5KK(eq->ax) 5.993006993-

%a(e) (low field; Cl eq) 14.3 

%b(a) (high field: Cl3 ax) 85.7 

DG(eq->ax) -1913.20864J mol-1

DG(eq->ax) -1.91320864kJ mol-1

DG(eq->ax) -0.45725687kcal mol-1

conversion factor 0.239kcal/kJkB 1.381E-23J K-1h 6.626E-34J s

R 8.315J K-1 mol-1

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

SiBr Si

Br

ax

eq

G

G#

(eq->#; see below)

kcal mol-1

DG#(eq->#)5.1528175.2509845.3541355.4622035.7723495.4657365.426652

Tc109.9131943113.1365063117.2489699123.0948716132.2453248141.0179753149.7396298

ksum152198299601930

1161343793

k(eq->ax) k(ax->eq)130.264 21.736169.686 28.314256.243 42.757515.057 85.943797.01 132.99

9952.341 1660.65937530.6 6262.399

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

6.0

5.8

5.6

5.4

5.2

5.0

4.8

4.6

145140135130125120115110 Tcorr

G#

G# = H# -TS# =>H# = 4.46 kcal mol-1; S# = +0.0075 kcal mol-1K-1 / +7.5 cal mol-1K-1

(eq->#)

Coefficient values ± one standard deviation a =4.4628 ± 0.618 b =0.0074972 ± 0.00485

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxp Lay:,0 Gr:0

5.412125 0.13669699Average: +/-

C3,C5 analysis:

6.0

5.8

5.6

5.4

5.2

5.0

4.8

4.6

145140135130125120115110

Or parabola fit:

Tcorr

G#

(eq->#)

Coefficient values ± one standard deviation K0 =-9.9887 ± 4.34 K1 =0.23347 ± 0.0677 K2 =-0.00087287 ± 0.000261

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxp Lay:,0 Gr:0

5.412125 0.13669699Average: +/-

C3,C5 analysis:

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxp Lay:,1 Gr:1

40

30

20

10

0

x10

3

9000 8900 8800 8700 8600 8500 8400 8300

TNMR [K] Tcorr [K]

160 149.7396

150 141.018

140 132.2453

130 123.0949

124 117.249

120 113.1365

117 109.9132

k(eq->ax):

130

170

260

520

800

10000

44000

Simulation:Red: exp./black dots: calc.

C3,C5

eq

ax

26 24 22 20 18 16

keq,ax(s-1 )

Calc.Exp.

T(K)

150

141

123

117

113

110

38000

10000

520

260

170

130