sch-i summary of spectra vs t, (slides: 3-7 (“hot”); 9-10(“cold”))

15
of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”)) s. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C4) 7,10) alysis for C3-C5 (slides: 12-15) : notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.ppt notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.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 I H Si I H

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SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”)) calc. vs. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C4) (slides 7,10) DNMR-analysis for C3-C5 (slides: 12-15) PPT´s: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.ppt IGOR´s: - PowerPoint PPT Presentation

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Page 1: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

SCH-I•Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))•calc. vs. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C4)(slides 7,10)•DNMR-analysis for C3-C5 (slides: 12-15)

PPT´s:https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.ppt IGOR´s:https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxpXLS´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

SiI

H

Si

I

H

Page 2: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

TNMR [K] z Tcorr [K] file names i: size/K190 -0.126871448 177.5581 SCH-Br-190-160712i b 64180 -0.315668246 167.8895 b 64168 -0.542224404 156.8409 b 64155 -0.787660241 145.3685 b 64150 -0.88205864 141.018 omerkt b 64146 -0.957577359 137.5312 a b 64142 -1.033096079 134.0182 3 b 64138 -1.108614798 130.4577 2 2 b 64138 -1.108614798 130.4577 b 64134 -1.184133517 126.8255 3 3 b 64134 -1.184133517 126.8255 2 2 b 64134 -1.184133517 126.8255 b 64130 -1.259652236 123.0949 b 64127 -1.316291276 120.2147 2 2 b 64127 -1.316291276 120.2147 b 64123 -1.391809995 116.2389 b 64

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

Page 3: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

600

400

200

0

-200

-400

30 25 20 15

TNMR [K] Tcorr [K]

190 177.5581

180 167.8895

168 156.8409

155 145.3685

150 141.018

146 137.5312

142 134.0182

138 130.4577138 130.4577

134 126.8255

134 126.8255

134 126.8255

130 123.0949

127 120.2147

127 120.2147

123 116.2389

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxp

C4 C3,C5 C2,C6

SCH-I

ppm

Page 4: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

TNMR [K] Tcorr [K]

190 177.5581

180 167.8895

168 156.8409

155 145.3685

150 141.018

146 137.5312

142 134.0182

138 130.4577138 130.4577

134 126.8255

134 126.8255

134 126.8255

130 123.0949

127 120.2147

127 120.2147

123 116.2389

600

400

200

0

-200

-400

17 16 15 14 13

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxp

SCH-I

ppm

C2,C6

Page 5: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

TNMR [K] Tcorr [K]

190 177.5581

180 167.8895

168 156.8409

155 145.3685

150 141.018

146 137.5312

142 134.0182

138 130.4577138 130.4577

134 126.8255

134 126.8255

134 126.8255

130 123.0949

127 120.2147

127 120.2147

123 116.2389

600

400

200

0

-200

-400

26 25 24 23

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxp

SCH-I

ppm

C3,C5

Page 6: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

TNMR [K] Tcorr [K]

190 177.5581

180 167.8895

168 156.8409

155 145.3685

150 141.018

146 137.5312

142 134.0182

138 130.4577138 130.4577

134 126.8255

134 126.8255

134 126.8255

130 123.0949

127 120.2147

127 120.2147

123 116.2389

600

400

200

0

-200

-400

31.5 31.0 30.5 30.0 29.5 29.0

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxp

SCH-I

ppm

C4

Page 7: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

-500

-400

-300

-200

35 30 25 20 15

Calc,ax.-eq = +0.33 -4.71 -3.12

C4 C3,C5 C2,C6

ppm

Page 8: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

Comments:

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

•Not clear what is the case for C4

NEW “Colder” spectra added:

Page 9: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

-600

-400

-200

0

200

400

600

30 25 20 15

TNMR [K] Tcorr [K]

190 177.5581

180 167.8895

168 156.8409

155 145.3685

150 141.018

146 137.5312

142 134.0182

138 130.4577138 130.4577

134 126.8255

134 126.8255

134 126.8255

130 123.0949

127 120.2147

127 120.2147

123 116.2389

TNMR [K] Tcorr [K]

140 132.2453

135 127.7416

131 124.0383

127 120.2147

123 116.2389

120 113.1365

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxp

SCH-I

ppm

Page 10: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

-700

-600

-500

-400

-300

-200

30 25 20 15

TNMR [K] Tcorr [K]

134 126.8255

130 123.0949

127 120.2147

127 120.2147

123 116.2389

131 124.0383

127 120.2147

123 116.2389

120 113.1365

https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-I-Sp.%20vs%20T-160712.pxp

SCH-I

ppm

eq

ax

Page 11: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

•Not very clear!

Page 12: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

parameter value unitR 8.315J K-1 mol-1<T> 128.5KK(eq->ax) 5.993007-%a(e) (low field; Cl eq) 14.3 %b(a) (high field: Cl3 ax) 85.7 DG(eq->ax) -1913.21J mol-1DG(eq->ax) -1.91321kJ mol-1DG(eq->ax) -0.45726kcal mol-1

conversion factor 0.239kcal/kJkB 1.38E-23J K-1h 6.63E-34J sR 8.315J K-1 mol-1

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

Si I Si

I

ax

eqG

G#

(eq->#; see below)

Page 13: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

C3,C5 analysis:

kcal mol-1DG#(eq->#)5.1320817545.3138706225.44398463

5.4939421375.534958685.67636064

Tc113.1365063116.2389281120.2146635124.0383143127.7416497132.2453248

ksum336289371631

10551340

k(eq->ax) k(ax->eq)287.952 48.048247.673 41.327317.947 53.053540.767 90.233904.135 150.8651148.38 191.62

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

130125120115Tcorr

G#

G# = H# -TS# =>H# = 2.32 kcal mol-1; S# = +0.0255 kcal mol-1K-1 / +25.5 cal mol-1K-1

(eq->#)

Average: +/-

Coefficient values ± one standard deviation a =2.3173 ± 0.412 b =0.025479 ± 0.00337

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

5.432533077 0.139705

Page 14: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

6.0

5.8

5.6

5.4

5.2

5.0

4.8

4.6

130125120115

Or parabola fit:

Tcorr

G#

(eq->#) Coefficient values ± one standard deviation K0 =-9.2672 ± 8 K1 =0.21499 ± 0.131 K2 =-0.00077285 ± 0.000533

C3,C5 analysis:

Average: +/-5.432533077 0.139705

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

Page 15: SCH-I Summary of spectra vs T, (slides: 3-7 (“hot”); 9-10(“cold”))

30

25

20

15

10

5

0

x103

9100 9000 8900 8800 8700 8600 8500 8400

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

TNMR [K] Tcorr [K]

140 132.2453

135 127.7416

131 124.0383

127 120.2147

123 116.2389

120 113.1365

k(eq->ax):Simulation:Red: exp./black dots: calc.

C3,C5

1100

900

540

320

250

290eq

ax