1. 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:
IGOR´s:
XLS´s : H Si I I Si H

2. TNMR [K] z
Tcorr [K]
file names i:
size/K
190
SCH-Br i b 64
180
168
155
150
omerkt
146 a
142 3
138 2
134
130
127
123

3. SCH-I C3,C5 C4 C2,C6 ppm TNMR [K] Tcorr [K] 190 177.5581 180 167.8895
168
155
150
146
142
138
134
130
127
123
C3,C5 C4
C2,C6
ppm

4. SCH-I C2,C6 ppm TNMR [K] Tcorr [K] 190 177.5581 180 167.8895 168
155
150
146
142
138
134
130
127
123
C2,C6
ppm

5. SCH-I C3,C5 ppm TNMR [K] Tcorr [K] 190 177.5581 180 167.8895 168
155
150
146
142
138
134
130
127
123
C3,C5
ppm

6. SCH-I C4 ppm TNMR [K] Tcorr [K] 190 177.5581 180 167.8895 168 156.8409
155
150
146
142
138
134
130
127
123 C4
ppm

7. Calc,
ax.-eq =
C3,C5
C2,C6 C4
ppm

8. NEW “Colder” spectra added:
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:

9. SCH-I ppm TNMR [K] Tcorr [K] 140 132.2453 135 127.7416 131 124.0383
123
120
TNMR [K]
Tcorr [K]
190
180
168
155
150
146
142
138
134
130
127
123
ppm

10. SCH-I
131
127
123
120
TNMR [K]
Tcorr [K]
134
130
127
123 ax eq
ppm

11. Not very clear!

12. DG# eq (eq->#; see below) G ax Si I Si I parameter value unit R
8.315
J K-1 mol-1
<T>
128.5 K
K(eq->ax) -
%a(e) (low field; Cl eq)
14.3
%b(a) (high field: Cl3 ax)
85.7
DG(eq->ax)
J mol-1
kJ mol-1
kcal mol-1
conversion factor
0.239
kcal/kJ kB
1.38E-23
J K-1 h
6.63E-34
J s
DG# eq
(eq->#; see below) G ax Si I Si I

13. C3,C5 analysis: DG# (eq->#) Average: +/- DG# = DH# -TDS# =>
kcal mol-1
DG#(eq->#) Tc
ksum
336
289
371
631
1055
1340
k(eq->ax)
k(ax->eq)
48.048
41.327
53.053
90.233
191.62
Coefficient values ± one standard deviation
a = ± 0.412
b = ±
DG#
(eq->#)
Average:
+/-
DG# = DH# -TDS# =>
DH# = 2.32 kcal mol-1; DS# = kcal mol-1K-1 / cal mol-1K-1
Tcorr
Lay: 0 Gr:0

14. Coefficient values ± one standard deviation K0 =-9.2672 ± 8
C3,C5 analysis:
Or parabola fit:
DG#
Coefficient values ± one standard deviation
K0 = ± 8
K1 = ± 0.131
K2 = ±
(eq->#)
Average:
+/-
Tcorr
Lay: 0 Gr:0

15. Red: exp./black dots: calc. C3,C5 k(eq->ax):
Simulation:
Red: exp./black dots: calc.
C3,C5
TNMR [K]
Tcorr [K]
140
135
131
127
123
120
k(eq->ax):
1100
900
540
320
250 ax eq
290
Lay: 1 Gr:1