sch-i summary of spectra vs t, (slides: 3-7 (“hot”); 9-10(“cold”))
DESCRIPTION
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 PresentationTRANSCRIPT
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
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
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
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
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
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
-500
-400
-300
-200
35 30 25 20 15
Calc,ax.-eq = +0.33 -4.71 -3.12
C4 C3,C5 C2,C6
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
NEW “Colder” spectra added:
-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
-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
•Not very clear!
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)
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
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
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