SCH-Cl Summary of spectra vs T, (slides: 3-7 (“hot”); 10-14 (“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: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.ppt PXP: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-030812.pxp https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp; XLS: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls H Si Cl Cl Si H

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 -0.22127 172.6678 SCH-Cl-185-150712i a 64 bgr correcton NOT needed 180 -0.31567 167.8895 170 -0.50447 158.6453 160 -0.69326 149.7396 156 -0.76878 146.2401 152 -0.8443 142.7576 148 -0.91982 139.2766 144 -0.99534 135.7792 140 -1.07086 132.2453 136 -1.14637 128.6521 132 -1.22189 124.9743 a,b 128 -1.29741 121.1835 125 -1.35405 118.2479 123 -1.39181 116.2389 a: NOT baseline corrected b: baseline corrected https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

SCH-Cl C4 C3,C5 C2,C6 ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170 158.6453 160 149.7396 156 146.2401 152 142.7576 148 139.2766 144 135.7792 140 132.2453 136 128.6521 132 124.9743 128 121.1835 125 118.2479 123 116.2389 C4 C3,C5 C2,C6 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp; Lay:0, Gr:0

SCH-Cl C2,C6 ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170 158.6453 160 149.7396 156 146.2401 152 142.7576 148 139.2766 144 135.7792 140 132.2453 136 128.6521 132 124.9743 128 121.1835 125 118.2479 123 116.2389 C2,C6 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp; Lay:0; Gr:0

SCH-Cl C3,C5 Eq. ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170 158.6453 160 149.7396 156 146.2401 152 142.7576 148 139.2766 144 135.7792 140 132.2453 136 128.6521 132 124.9743 128 121.1835 125 118.2479 123 116.2389 C3,C5 Eq. ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp

SCH-Cl C4 ppm TNMR [K] Tcorr [K] 185 172.6678 180 167.8895 170 158.6453 160 149.7396 156 146.2401 152 142.7576 148 139.2766 144 135.7792 140 132.2453 136 128.6521 132 124.9743 128 121.1835 125 118.2479 123 116.2389 C4 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp

Calc, ax.-eq = +0.35 -3.11 -1.46 C4 C3,C5 C2,C6 ppm 132 124.9743 128 121.1835 125 118.2479 123 116.2389 Calc, ax.-eq = +0.35 -3.11 -1.46 C4 C3,C5 C2,C6 ppm Calc,: https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp /C:... ibrcl-silacyclo-nmr.xlsx

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):

C2,C6 C3,C5 C4 170/158.6 D= -1.95 ppm; exp. 123/116.2 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-150712.pxp; Lay:1, Gr:1

SCH-Cl; NEW TNMR [K] Tcorr [K] 180 167.8895 170 158.6453 160 149.7396 154 144.4977 150 2 141.018 146 137.5312 142 134.0182 138 130.4577 134 126.8255 129 122.1434 126 119.2363 123 116.2389 120 113.1365 118 111.0021 116 108.809 115 107.6889 C4 C3,C5 C2,C6 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-030812.pxp ; Lay:2, Gr:2

SCH-Cl; NEW TNMR [K] Tcorr [K] 180 167.8895 170 158.6453 160 149.7396 154 144.4977 150 2 141.018 146 137.5312 142 134.0182 138 130.4577 134 126.8255 129 122.1434 126 119.2363 123 116.2389 120 113.1365 118 111.0021 116 108.809 115 107.6889 C2,C6 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-030812.pxp ; Lay:2, Gr:2

SCH-Cl; NEW TNMR [K] Tcorr [K] 180 167.8895 170 158.6453 160 149.7396 154 144.4977 150 2 141.018 146 137.5312 142 134.0182 138 130.4577 134 126.8255 129 122.1434 126 119.2363 123 116.2389 120 113.1365 118 111.0021 116 108.809 115 107.6889 C3,C5 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-030812.pxp ; Lay:2, Gr:2

SCH-Cl; NEW TNMR [K] Tcorr [K] 180 167.8895 170 158.6453 160 149.7396 154 144.4977 150 2 141.018 146 137.5312 142 134.0182 138 130.4577 134 126.8255 129 122.1434 126 119.2363 123 116.2389 120 113.1365 118 111.0021 116 108.809 115 107.6889 C4 ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-030812.pxp ; Lay:2, Gr:2

SCH-Cl; NEW Calc, ax.-eq = +0.35 -3.11 -1.46 C3,C5 C4 C2,C6 -2.319 TNMR [K] Tcorr [K] 120 113.1365 118 2 111.0021 116 108.809 115 107.6889 Calc, ax.-eq = +0.35 -3.11 -1.46 C3,C5 C4 C2,C6 22.57992 ppm 24.89422 ppm -2.319 -1.09 Exp.: ax.-eq ppm https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-Sp.%20vs%20T-030812.pxp ; Lay:2, Gr:2

Red: exp./black dots: calc. C3,C5 Simulation: Red: exp./black dots: calc. C3,C5 TNMR [K] Tcorr [K] 180 167.8895 170 158.6453 160 149.7396 154 144.4977 150 141.018 146 137.5312 142 134.0182 138 130.4577 134 126.8255 129 122.1434 126 119.2363 123 116.2389 120 113.1365 118 111.0021 116 108.809 115 107.6889 k(eq->ax): : 25000 12000 7000 4300 2400 990 610 430 270 180 160 130 ax eq : Hz https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:0,Gr:0

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-040812.pxp 1 40812 SCH-Cl-T DNMR 2 Spin (sch-cl-115-030812b.nts) w0-3 115 107.6889 DNMR 2 Spin (sch-cl-116-2-030812b.nts) 6000 w4-7 116-2 108.809 3 DNMR 2 Spin (sch-cl-118-2-030812b.nts) 12000 w-8-13_error incl. 118-2 111.0021 4 DNMR 2 Spin (sch-cl-120-030812b.nts) 18000 w-14-17 120 113.1365 5 DNMR 2 Spin (sch-cl-123-030812b.nts) 24000 w-18-21 123 116.2389 6 DNMR 2 Spin (sch-cl-126-030812b.nts) 30000 w-22-25 126 119.2363 7 DNMR 2 Spin (sch-cl-129-030812b.nts) 36000 w-26-29 129 122.1434 8 DNMR 2 Spin (sch-cl-134-030812b.nts) w-30-33 134 126.8255 9 DNMR 2 Spin (sch-cl-138-030812b.nts) w-34-37 138 130.4577 10 DNMR 2 Spin (sch-cl-142-030812b.nts) w-38-41 142 134.0182 11 DNMR 2 Spin (sch-cl-146-030812b.nts) 60000 w-42-45 146 137.5312 12 DNMR 2 Spin (sch-cl-150-030812b.nts) 66000 w-46-49 150 141.018 13 DNMR 2 Spin (sch-cl-154-030812b.nts) 72000 w-50-53 154 144.4977 14 DNMR 2 Spin (sch-cl-134a-030812b.nts) 42000 w-54-57 15 DNMR 2 Spin (sch-cl-138a-030812b.nts) 48000 w-58-61 16 DNMR 2 Spin (sch-cl-142a-030812b.nts) 54000 w-62-65 17 50812 DNMR 2 Spin (sch-cl-160-030812b.nts) 78000 w-66-69 160 149.7396 18 DNMR 2 Spin (sch-cl-170-030812b.nts) 84000 w-70-73 170 158.6453 19 DNMR 2 Spin (sch-cl-180-030812b.nts) 90000 w-74-77 180 167.8895 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 3000000 43.1 18 8737.5 8503.2 mjög hátt! 2.5 45.6 19 8740.5 8506.2 48 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

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) 4.882352941 - %a(e) (low field; Cl eq) 17   %b(a) (high field: Cl3 ax) 83 DG(eq->ax) -1694.20705 J mol-1 -1.69420705 kJ mol-1 -0.40491549 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 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls

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->#) 5.051015 5.108655 5.161568 5.23758 5.294858 5.327155 5.378008 5.470532 5.406758 5.405289 5.420566 5.415538 5.341 4.178358   Tc 107.6888768 108.8090089 111.0020831 113.1365063 116.2389281 119.2362942 122.1434444 126.8254686 130.4576616 134.0182064 137.5311554 141.0179753 144.4976642 149.7396298 ksum 152 150 192 217 324 516 732 1193 2872 5163 8414 14343 30343 3000000 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 2383.76 488.24 4285.29 877.71 6983.62 1430.38 11904.69 2438.31 25184.69 5158.31 2490000 510000 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls Coefficient values ± one standard deviation a =4.2801 ± 0.238 b =0.0082956 ± 0.00191 DG# (eq->#) Average: +/- 5.309117 0.106448 DG# = DH# -TDS# => DH# = 4.28 kcal mol-1; DS# = +0.0083 kcal mol-1K-1 / +8.3 cal mol-1K-1 Tcorr https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:1,Gr:4

Coefficient values ± one standard deviation K0 =-5.4913 ± 0.902 C3,C5 analysis: Or parabola fit: DG# (eq->#) Coefficient values ± one standard deviation K0 =-5.4913 ± 0.902 K1 =0.16564 ± 0.0145 K2 =-0.00062742 ± 5.77e-005 Average: +/- 5.309117 0.106448 Tcorr https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:1,Gr:4

How does this compair with SCH-F?: https://notendur.hi.is/agust/rannsoknir/papers/organom26-6544-07.pdf : vs SCH-Cl (see above): 128.5 NMR -0.40 83 SCH-F:

Coefficient values ± one standard deviation DG# (eq->#) C2,C6 analysis: kcal mol-1 DG#(eq->#) 5.053850817 5.056404216 5.119823178 5.181882801 5.271805584 5.35801021 5.431590695 5.410476837 5.322627922 5.316716032 4.90251404 Tc 107.6889 108.809 111.0021 113.1365 116.2389 119.2363 122.1434 126.8255 130.4577 134.0182 137.5312 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 1256.62 257.38 3297.59 675.41 5976 1224 46480 9520 https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-X-Sp.%20vs%20T-150712.xls Coefficient values ± one standard deviation a =3.8139 ± 0.392 b =0.012092 ± 0.00329 DG# (eq->#) Average: 5.220518394 +/-0.143293985 DG# = DH# -TDS# => DH# = 3.81 kcal mol-1; DS# = +0.012 kcal mol-1K-1 / +12 cal mol-1K-1 Tcorr https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:2 Gr:5

C2,C6 analysis: Or parabola fit: DG# (eq->#) Average: Tcorr Coefficient values ± one standard deviation K0 =-13.65 ± 2.49 K1 =0.30369 ± 0.0416 K2 =-0.0012106 ± 0.000172 Average: 5.220518394 +/-0.143293985 Tcorr https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:2,Gr:5

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] 146 137.5312 142 134.0182 138 130.4577 134 126.8255 129 122.1434 126 119.2363 123 116.2389 120 113.1365 118 111.0021 116 108.809 115 107.6889 k(eq->ax): 46000 6000 3300 1300 490 380 300 230 190 160 ax eq 120 Hz https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:3,Gr:6

Exp. Calc. keq,ax/s-1 T(K) 144 25000 134 4300 127 990 122 610 116 270 108 125 Dd https://notendur.hi.is/agust/rannsoknir/SCH/July12/SCH-Cl-T-040812.pxp ;Lay:4,Gr:8