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SCH-Cl Summary of spectra vs T, (slides: 3-7 (“hot”); (“cold”)) calc. vs. exp. chemical shift differences for ax.-eq. (C2-C6, C3-C5, C4) (slides 7,9,14) DNMR-analysis for C3-C5 (slides: 15-19) DNMR-analysis for C2-C6 (slides: 21-22): PPT: PXP: XLS: H Si Cl Cl Si H
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Enter the temperature as given by the NMR instrument into a cell in the TNMR column and the values for z and Tcorr will be automatically calculated. nuts and txt- TNMR [K] z Tcorr [K] file names i: size/K 185 SCH-Cl i a 64 bgr correcton NOT needed 180 170 160 156 152 148 144 140 136 132 a,b 128 125 123 a: NOT baseline corrected b: baseline corrected
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SCH-Cl C4 C3,C5 C2,C6 ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895
170 160 156 152 148 144 140 136 132 128 125 123 C4 C3,C5 C2,C6 ppm Lay:0, Gr:0
![SCH-Cl C4 C3,C5 C2,C6 ppm TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/3/SCH-Cl+C4+C3%2CC5+C2%2CC6+ppm+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C4. C3,C5. C2,C6. ppm. Lay:0, Gr:0.")
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SCH-Cl C2,C6 ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170
160 156 152 148 144 140 136 132 128 125 123 C2,C6 ppm Lay:0; Gr:0
![SCH-Cl C2,C6 ppm TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/4/SCH-Cl+C2%2CC6+ppm+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C2,C6. ppm. Lay:0; Gr:0.")
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SCH-Cl C3,C5 Eq. ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170
160 156 152 148 144 140 136 132 128 125 123 C3,C5 Eq. ppm
![SCH-Cl C3,C5 Eq. ppm TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/5/SCH-Cl+C3%2CC5+Eq.+ppm+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C3,C5. Eq. ppm.")
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SCH-Cl C4 ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170
160 156 152 148 144 140 136 132 128 125 123 C4 ppm
![SCH-Cl C4 ppm TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/6/SCH-Cl+C4+ppm+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C4. ppm.")
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Calc, ax.-eq = +0.35 -3.11 -1.46 C4 C3,C5 C2,C6 ppm 132 124.9743 128
125 123 Calc, ax.-eq = C4 C3,C5 C2,C6 ppm Calc,: /C:... ibrcl-silacyclo-nmr.xlsx
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See NEW, “Colder” spectra below (slides 10 – 14):
Comments: Chemical shift calculations seem to overestimate abs(ax.-eq.) spacings for C2/C6 & C3/C5 Although not very clear, it seems to be that eq. > ax according to exp. but calculations predict the opposide for C4(?) Only possible to determne chemical shift for eq. For C3,C5 Further cooling needed to determine chemical shifts for eq. For C2,C6 and C4 See NEW, “Colder” spectra below (slides 10 – 14):
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C2,C6 C3,C5 C4 170/158.6 D= -1.95 ppm; exp. 123/116.2 ppm
Lay:1, Gr:1
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SCH-Cl; NEW TNMR [K] Tcorr [K] 180 170 160 154 150 2 146 142 138 134 129 126 123 120 118 116 115 C4 C3,C5 C2,C6 ppm ; Lay:2, Gr:2
![SCH-Cl; NEW TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/10/SCH-Cl%3B+NEW+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C4. C3,C5. C2,C6. ppm. ; Lay:2, Gr:2.")
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SCH-Cl; NEW TNMR [K] Tcorr [K] 180 170 160 154 150 2 146 142 138 134 129 126 123 120 118 116 115 C2,C6 ppm ; Lay:2, Gr:2
![SCH-Cl; NEW TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/11/SCH-Cl%3B+NEW+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C2,C6. ppm. ; Lay:2, Gr:2.")
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SCH-Cl; NEW TNMR [K] Tcorr [K] 180 170 160 154 150 2 146 142 138 134 129 126 123 120 118 116 115 C3,C5 ppm ; Lay:2, Gr:2
![SCH-Cl; NEW TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/12/SCH-Cl%3B+NEW+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C3,C5. ppm. ; Lay:2, Gr:2.")
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SCH-Cl; NEW TNMR [K] Tcorr [K] 180 170 160 154 150 2 146 142 138 134 129 126 123 120 118 116 115 C4 ppm ; Lay:2, Gr:2
![SCH-Cl; NEW TNMR [K] Tcorr [K]](http://slideplayer.com./slide/15480054/93/images/13/SCH-Cl%3B+NEW+TNMR+%5BK%5D+Tcorr+%5BK%5D.jpg "C4. ppm. ; Lay:2, Gr:2.")
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SCH-Cl; NEW Calc, ax.-eq = +0.35 -3.11 -1.46 C3,C5 C4 C2,C6 -2.319
TNMR [K] Tcorr [K] 120 118 2 116 115 Calc, ax.-eq = C3,C5 C4 C2,C6 ppm ppm -2.319 -1.09 Exp.: ax.-eq ppm ; Lay:2, Gr:2
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Red: exp./black dots: calc. C3,C5
Simulation: Red: exp./black dots: calc. C3,C5 TNMR [K] Tcorr [K] 180 170 160 154 150 146 142 138 134 129 126 123 120 118 116 115 k(eq->ax): : 25000 12000 7000 4300 2400 990 610 430 270 180 160 130 ax eq : Hz ;Lay:0,Gr:0
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C3,C5 analysis: n0 date Sim-Group SimSave offset waves in IGOR Tm Tc
SCH-Cl n0 date Sim-Group SimSave offset waves in IGOR Tm Tc SCH-Cl-T pxp 1 40812 SCH-Cl-T DNMR 2 Spin (sch-cl b.nts) w0-3 115 DNMR 2 Spin (sch-cl b.nts) 6000 w4-7 116-2 3 DNMR 2 Spin (sch-cl b.nts) 12000 w-8-13_error incl. 118-2 4 DNMR 2 Spin (sch-cl b.nts) 18000 w-14-17 120 5 DNMR 2 Spin (sch-cl b.nts) 24000 w-18-21 123 6 DNMR 2 Spin (sch-cl b.nts) 30000 w-22-25 126 7 DNMR 2 Spin (sch-cl b.nts) 36000 w-26-29 129 8 DNMR 2 Spin (sch-cl b.nts) w-30-33 134 9 DNMR 2 Spin (sch-cl b.nts) w-34-37 138 10 DNMR 2 Spin (sch-cl b.nts) w-38-41 142 11 DNMR 2 Spin (sch-cl b.nts) 60000 w-42-45 146 12 DNMR 2 Spin (sch-cl b.nts) 66000 w-46-49 150 13 DNMR 2 Spin (sch-cl b.nts) 72000 w-50-53 154 14 DNMR 2 Spin (sch-cl-134a b.nts) 42000 w-54-57 15 DNMR 2 Spin (sch-cl-138a b.nts) 48000 w-58-61 16 DNMR 2 Spin (sch-cl-142a b.nts) 54000 w-62-65 17 50812 DNMR 2 Spin (sch-cl b.nts) 78000 w-66-69 160 18 DNMR 2 Spin (sch-cl b.nts) 84000 w-70-73 170 19 DNMR 2 Spin (sch-cl b.nts) 90000 w-74-77 180 no Va Vb DV kab+kba Wa Wb %a error comment Right-Hz WidthHz 1 8717.5 8483.2 234.3 152 5.5 17 68.4 good fit 8178.9 815.11 8722.5 8488.2 150 58.6 3 8723.4 8489.1 192 39.9 4 8726.5 8492.2 217 59.2 5 8729.5 8495.2 324 20.7 6 8728.5 8494.2 516 39.6 7 732 20.5 8 8732.5 8501.2 231.3 1193 27.3 9 8727.5 8496.2 2789 31.7 10 8497.2 5083 49.7 11 8730.5 8499.2 8414 55 12 14343 67.9 13 8498.2 30343 78.4 14 8735.5 27.6 15 2872 34 16 8731.5 5163 47.6 8734.5 8500.2 43.1 18 8737.5 8503.2 mjög hátt! 2.5 45.6 19 8740.5 8506.2 48
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C3,C5 analysis: DG# eq (eq->#; see below) G ax Si Cl Si Cl
parameter value unit R 8.315 J K-1 mol-1 <T> 128.5 K K(eq->ax) - %a(e) (low field; Cl eq) 17 %b(a) (high field: Cl3 ax) 83 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 T range: 107 to 150 DG# eq (eq->#; see below) G ax Si Cl Si Cl
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DH# = 4.28 kcal mol-1; DS# = +0.0083 kcal mol-1K-1 / +8.3 cal mol-1K-1
C3,C5 analysis: kcal mol-1 DG#(eq->#) 5.341 Tc ksum 152 150 192 217 324 516 732 1193 2872 5163 8414 14343 30343 k(eq->ax) k(ax->eq) 126.16 25.84 124.5 25.5 159.36 32.64 180.11 36.89 268.92 55.08 428.28 87.72 607.56 124.44 990.19 202.81 488.24 877.71 510000 Coefficient values ± one standard deviation a = ± 0.238 b = ± DG# (eq->#) Average: +/- DG# = DH# -TDS# => DH# = 4.28 kcal mol-1; DS# = kcal mol-1K-1 / +8.3 cal mol-1K-1 Tcorr ;Lay:1,Gr:4
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Coefficient values ± one standard deviation K0 =-5.4913 ± 0.902
C3,C5 analysis: Or parabola fit: DG# (eq->#) Coefficient values ± one standard deviation K0 = ± 0.902 K1 = ± K2 = ± 5.77e-005 Average: +/- Tcorr ;Lay:1,Gr:4
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How does this compair with SCH-F?:
: vs SCH-Cl (see above): NMR SCH-F:
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Coefficient values ± one standard deviation DG# (eq->#)
C2,C6 analysis: kcal mol-1 DG#(eq->#) Tc ksum 150 191 232 278 358 453 587 1514 3973 7200 56000 k(eq->ax) k(ax->eq) 124.5 25.5 158.53 32.47 192.56 39.44 230.74 47.26 297.14 60.86 375.99 77.01 487.21 99.79 257.38 675.41 5976 1224 46480 9520 Coefficient values ± one standard deviation a = ± 0.392 b = ± DG# (eq->#) Average: +/ DG# = DH# -TDS# => DH# = 3.81 kcal mol-1; DS# = kcal mol-1K-1 / +12 cal mol-1K-1 Tcorr ;Lay:2 Gr:5
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C2,C6 analysis: Or parabola fit: DG# (eq->#) Average: Tcorr
Coefficient values ± one standard deviation K0 = ± 2.49 K1 = ± K2 = ± Average: +/ Tcorr ;Lay:2,Gr:5
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Red: exp./black dots: calc. C2,C6 analysis: k(eq->ax): 46000
Simulation: Red: exp./black dots: calc. C2,C6 analysis: TNMR [K] Tcorr [K] 146 142 138 134 129 126 123 120 118 116 115 k(eq->ax): 46000 6000 3300 1300 490 380 300 230 190 160 ax eq 120 Hz ;Lay:3,Gr:6
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Exp. Calc. keq,ax/s-1 T(K) 144 25000 134 4300 127 990 122 610 116 270 108 125 Dd ;Lay:4,Gr:8
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