1. 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.ppthttps://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 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 Si Br H Si Br H

2. nuts and txt- TNMR [K]zTcorr [K]file namesi:size/K 180-0.31566825167.889512SCH-Br-180-150712ib64 170-0.50446504158.645267b64 160-0.69326184149.73963b64 156-0.76878056146.240126b64 152-0.84429928142.757617b64 148-0.919818139.276588b64 144-0.99533672135.77923b64 140-1.07085544132.245325b64 136-1.14637416128.652129b64 132-1.22189288124.974252b64 128-1.2974116121.183542b64 124-1.37293032117.24897b64 highb64 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

3. TNMR [K]Tcorr [K] high 180167.889512 170158.645267 160149.73963 156146.240126 152142.757617 148139.276588 144135.77923 140132.245325 136128.652129 132124.974252 128121.183542 124117.24897 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp C4 C3,C5 C2,C6 ppm SCH-Br

4. TNMR [K]Tcorr [K] high 180167.889512 170158.645267 160149.73963 156146.240126 152142.757617 148139.276588 144135.77923 140132.245325 136128.652129 132124.974252 128121.183542 124117.24897 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp C2,C6 ppm SCH-Br

5. TNMR [K]Tcorr [K] high 180167.889512 170158.645267 160149.73963 156146.240126 152142.757617 148139.276588 144135.77923 140132.245325 136128.652129 132124.974252 128121.183542 124117.24897 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp ppm SCH-Br C3,C5 eq. ax. X X

6. TNMR [K]Tcorr [K] high 180167.889512 170158.645267 160149.73963 156146.240126 152142.757617 148139.276588 144135.77923 140132.245325 136128.652129 132124.974252 128121.183542 124117.24897 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp ppm SCH-Br C4

7. 132124.974252 128121.183542 124117.24897 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

8. 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. For C3,C5 Further cooling needed to determine chemical shifts for eq. For C2,C6 and C4 New “colder” spectra added:

9. https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp ppm TNMR [K]Tcorr [K] high 180167.889512 170158.645267 160149.73963 156146.240126 152142.757617 148139.276588 144135.77923 140132.245325 136128.652129 132124.974252 128121.183542 124117.24897 C4 C3,C5C2,C6 SCH-Br TNMR [K]Tcorr [K] 160149.7396 150141.018 140132.2453 130123.0949 124117.249 120113.1365 117109.9132

10. https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxphttps://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp, Layout:0, Gr:0 ppm C4 C3,C5C2,C6 SCH-Br TNMR [K]Tcorr [K] 130123.0949 124117.249 120113.1365 117109.9132 132124.974252 128121.183542 124117.24897 eq

11. https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-Sp.%20vs%20T-150712.pxp ppm C4 C3,C5C2,C6 SCH-Br 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] 124117.249 120113.1365 117109.9132 22.89449 ppm 25.78859 ppm

12. parametervalueunit R8.315J K-1 mol-1 128.5K K(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 factor0.239kcal/kJ kB1.381E-23J K-1 h6.626E-34J s R8.315J K-1 mol-1 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls Si Br Si Br ax eq G G#G# (eq->#; see below)

13. kcal mol-1 DG#(eq->#) 5.152817 5.250984 5.354135 5.462203 5.772349 5.465736 5.426652 Tc 109.9131943 113.1365063 117.2489699 123.0948716 132.2453248 141.0179753 149.7396298 ksum 152 198 299 601 930 11613 43793 k(eq->ax)k(ax->eq) 130.26421.736 169.68628.314 256.24342.757 515.05785.943 797.01132.99 9952.3411660.659 37530.66262.399 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls T corr G#G#  G # =  H # -T  S # =>  H # = 4.46 kcal mol -1 ;  S # = +0.0075 kcal mol -1 K -1 / +7.5 cal mol -1 K -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.pxphttps://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxp Lay:,0 Gr:0 5.4121250.13669699 Average:+/- C3,C5 analysis:

14. Or parabola fit: T corr G#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.pxphttps://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxp Lay:,0 Gr:0 5.4121250.13669699 Average:+/- C3,C5 analysis:

15. https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxphttps://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Br-T-080812.pxp Lay:,1 Gr:1 TNMR [K]Tcorr [K] 160149.7396 150141.018 140132.2453 130123.0949 124117.249 120113.1365 117109.9132 k(eq->ax): 130 170 260 520 800 10000 44000 Simulation: Red: exp./black dots: calc. C3,C5 eq ax

16. k eq,ax (s -1 ) Calc.Exp. T(K) 150 141 123 117 113 110 38000 10000 520 260 170 130