sch-br summary of spectra vs t, (slides: 3-7 (“hot”); 10-11(“cold”))
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 PresentationTRANSCRIPT
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