SCHt Bu working procedure update 140419 https notendur

SCH-t. Bu; working procedure; update: 140419 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PPT-140415. pptx https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140415. xls https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140416. xlsx Mynd: https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140416. xlsx

I. MESTRE-C procedure for creating NMR spectra from Fid´s according to http: //www 3. hi. is/~agust/kennsla/ee 10/ees 10/PPT/ees-DNMR-10. ppt : „nuts files (necessary input files for WINDNMR) are created with Mestre C as (inside Mestre C): File->import spectra->. . schsih 3 -> FID gogn-> Select for example sow 417 mr. 163 ->open->FT -> 256 K->Apply along t 1 -> Phase correction(if needed): select region of interest by using magnifying glass(+) and click and drag untill satisfactory-> press phase correction button->click mouse as said and hold and drag up or down and you will see the phase change; stop when it is good ->OK->File->Export file -> nuts->. . . appropriate file-> type name: schsih 3 -163. nts->save

CH 3´s C 2, C 6 „tertiary carbon“ T(NMR), Tcorr 132, 125 „tertiary carbon“ T(NMR), Tcorr 165, 154 125, 118 152, 143 120, 113 140, 132 139, 131 132, 125 118, 111 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp; Lay 0, Gr 0 / Lay 1, Gr 1 ppm 125, 118

CH 3´s C 2, C 6 „tertiary carbon“ T(NMR), Tcorr 132, 125, 118 C 2, C 6 T(NMR), Tcorr 165, 154 120, 113 152, 143 140, 132 139, 131 118, 111 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp; Lay 0, Gr 0 / Lay 2, Gr 2 ppm 132, 125

CH 3´s C 2, C 6 „tertiary carbon“ CH 3´s T(NMR), Tcorr 132, 125 179, 167 165, 154 125, 118 120, 113 152, 143 140, 132 139, 131 118, 111 132, 125, 118 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp; Lay 0, Gr 0 / Lay 3, Gr 3 ppm

„tertiary carbon“ CH 3´s T(NMR), Tcorr 179, 167 165, 154 „tertiary carbon“ T(NMR), Tcorr 165, 154 152, 143 140, 132 139, 131 D = 0. 046 ppm 132, 125, 118 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp; ppm Lay 3, Gr 3 / Lay 1, Gr 1 D = 0. 046 ppm 139, 131 132, 125, 118 ppm

C 2, C 6 T(NMR), Tcorr 165, 154 152, 143 140, 132 139, 131 D = 0. 044 ppm 132, 125 ppm https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp; Lay 2, Gr 2

TNMR [K] z Tcorr [K] 117, 0 -1, 505 109, 9 118, 0 -1, 486 111, 0 120, 0 -1, 448 113, 1 125, 0 -1, 354 118, 2 132, 0 -1, 222 125, 0 139, 0 -1, 090 131, 4 140, 0 -1, 071 132, 2 152, 0 -0, 844 142, 8 165, 0 -0, 599 154, 2 179, 0 -0, 335 166, 9 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140415. xls

Úr MS-ritgerð Nönnu R. Jónsdóttur, p: 32 (NB: toppum hefur verið hliðrað): http: //skemman. is/en/stream/get/1946/13944/33497/1/master. pdf

Geometries: B 3 LYP-D 3 BJ From Ragnar: PBE 1 PBE NMR calculations NMR basis: aug-pc. S-2 on C def 2 -TZVP on Si and H ax No. TMS Shielding Chemical shift 1 152, 3661 34, 1336 2 156, 9102 29, 5895 3 175, 444 11, 0557 5 175, 4724 11, 0273 6 156, 889 29, 6107 18 163, 8013 22, 6984 19 23 27 TBu-Me. Average 155, 3005 156, 2107 156, 2268 155, 912667 186, 4997 ppm eq No. 31, 1992 30, 289 30, 2729 30, 5870333 https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140416. xlsx Shielding Chemical shift 1 152, 1557 34, 344 2 156, 5814 29, 9183 3 175, 3318 11, 1679 5 175, 332 11, 1677 6 156, 5811 29, 9186 18 165, 539 20, 9607 19 23 27 TBu-Me. Average Difference 0, 2104 0, 3288 0, 1122 0, 1404 0, 3079 -1, 7377 156, 9364 156, 9357 158, 4272 29, 5633 29, 564 28, 0725 -1, 6359 -0, 725 -2, 2004 157, 4331 29, 0666 -1, 5204333

• It looks as if the observed Dd(ax-eq) values are a lot smaller than the predicted values

Need to download Win. DNMR according to: http: //www. chem. wisc. edu/areas/reich/plt/windnmr. htm NB: Use password given in 2009 It is working OK

Splitting (ax-eq (? )) is seen in all 13 C signals (t. Bu-C, the CH 3´s, C 2/C 6, C 3/C 5 and C 4) for T(NMR) = 132 (Tcorr=125 K); the splitting being only slightly different in magnitude: t. Bu-C: CH 3´s C 2, C 6: C 3, C 5: C 4: 5. 2 Hz; 0. 052 ppm 6. 3 Hz; 0. 063 ppm 5. 7 Hz; 0. 057 ppm 5. 9 Hz; 0. 059 ppm 6. 5 Hz; 0. 065 ppm -this contradicts Ragnars chemical shift calculations(? !) https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140415. xls

T(NMR)=132/Tcorr=125 K D(e-a) Hz 6. 5 %e 38 kab+kba s-1 18 C 3, C 5 5. 9 40 14 C 2, C 6 5. 7 39 13 t. Bu-C 5. 2 38 9 CH 3´s 6. 3 40 <39> 18 <14. 4> Exp. C 4…… Dn/Hz https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/PXP-140415. pxp; Lay 4, Gr 5 Calc. https: //notendur. hi. is/agust/rannsoknir/SCH/Jan 14/XLS-140415. xls