1. GeCH-Me
Summary of spectra vs T, DNMR analysis and figure for publication
PPT:
PXP:
XLS: H Ge Me Me Ge H

2. GeCH-Me Tm = 184 Tc = 171.7 K C3, C5 C2, C6 & impurities: GeCH

3. TNMR [K]
Tcorr [K]
184.0
171.7
170.0
158.6
160.0
149.7
150.0
141.0
142.0
134.0
136.0
128.7
132.0
125.0
128.0
121.2
124.0
117.2
121.0
114.2
119.0
112.1
117.0
109.9
115.5
108.3
114.0
106.6
113.5
106.0
C3, C5
C2, C6 Me C4
; Lay:0, Gr:0

4. TNMR [K]
Tcorr [K]
184.0
171.7
170.0
158.6
160.0
149.7
150.0
141.0
142.0
134.0
136.0
128.7
132.0
125.0
128.0
121.2
124.0
117.2
121.0
114.2
119.0
112.1
117.0
109.9
115.5
108.3
114.0
106.6
113.5
106.0
C2,C6
; Lay:0, Gr:0

5. TNMR [K]
Tcorr [K]
184.0
171.7
170.0
158.6
160.0
149.7
150.0
141.0
142.0
134.0
136.0
128.7
132.0
125.0
128.0
121.2
124.0
117.2
121.0
114.2
119.0
112.1
117.0
109.9
115.5
108.3
114.0
106.6
113.5
106.0
C3,C5
; Lay:0, Gr:0

6. TNMR [K]
Tcorr [K]
184.0
171.7
170.0
158.6
160.0
149.7
150.0
141.0
142.0
134.0
136.0
128.7
132.0
125.0
128.0
121.2
124.0
117.2
121.0
114.2
119.0
112.1
117.0
109.9
115.5
108.3
114.0
106.6
113.5
106.0 C4
; Lay:0, Gr:0

7. TNMR [K]
Tcorr [K]
142.0
134.0
136.0
128.7
132.0
125.0
128.0
121.2
124.0
117.2
121.0
114.2
119.0
112.1
117.0
109.9
115.5
108.3
114.0
106.6
113.5
106.0 Me
; Lay:0, Gr:0

8. The spectra for Me look most promishing
To determine rate- and
(thermo)dynamic parameters

9. Not easy to distinguish between eq. and ax.
C3,C5
Closer look
Not easy to distinguish
between eq. and ax.
TNMR [K]
Tcorr [K]
128.0
121.2
124.0
117.2
121.0
114.2
119.0
112.1
117.0
109.9
115.5
108.3
114.0
106.6
113.5
106.0
ppm
; Lay:0, Gr:0

10. Chemical shift / shielding calc (RB):ax
Atom numb.
isotr. Shield
delta 2 C 3 4 5 6 18 eq
Atom numb.
isotr. Shield
delta 2 C 3 4 5 6 17

11. RB´s prediction: Dd = 4.24 ppm -5.08 -9.33 shifted Dd = 3.47 ppm
<= spectrum
; Lay:0, Gr:0

12. Dd = 3.47 ppm (<= spectra analysis)

13. DG# eq (eq->#; see below) G ax Ge Me Ge Me parameter value unit R
8.315
J K-1 mol-1
<T>
114 K
K(eq->ax) -
%a(e) (low field; eq)
56.3
%b(a) (high field: ax)
43.7
DG(eq->ax)
J mol-1
kJ mol-1
kcal mol-1
conversion factor
0.239
kcal/kJ kB
1.381E-23
J K-1 h
6.626E-34
J s
DG# eq
(eq->#; see below) G ax Ge Me Ge Me

14. Coefficient values ± one standard deviation a =3.9244 ± 0.123
Me analysis:
k(sum)
kcal mol-1 Tc
k(eq->ax)
k(ax->eq)
sum check
DG#(eq->#)
556
711
908
1222
721.05
928.95
1650
2781
1966.5
2533.5
4500
3801.9
4898.1
8700
6205.4
7994.6
14200
34900
DG#
(eq->#)
Coefficient values ± one standard deviation
a = ± 0.123
b = ±
DG# = DH# -TDS# =>
DH# = 3.92 kcal mol-1; DS# = kcal mol-1K-1 / +8.9 cal mol-1K-1
Tcorr
; Gr:2

15. Coefficient values ± one standard deviation K0 =-1.5923 ± 0.57
Me analysis:
DG#
(eq->#)
Coefficient values ± one standard deviation
K0 = ± 0.57
K1 = ±
K2 = ± 4.04e-005
Tcorr +/
Average:
Gr:2

16. Analysis results:
K (eq -> ax):
DG(eq ->ax): kcal /mol (for T = 114 K)
Average DG# (eq->#):
5.0 +/- 0.1 kcal/mol (4.97 +/ kcal/mol) for
temperature range 106 – 134 K
Figure for publication (next slide):

17. Exp. Calc. Dd/ppm T(K) keq,ax(s-1 ) 125 117 114 112 110 107 3800 1200
720
530
400
240
Dd/ppm