Supporting Information for:

Complexes of TrimethylsilylTrifluoromethanesulfonate with N, O and P Donors

Alasdair P. M. Robertson,aSaurabhS. Chitnis,aSeth Chhina,a Hector J. Cortes S.,aBrian O. Patrick,bHilary A. Jenkinsc and Neil Burford*a

aDepartment of Chemistry, University of Victoria, P.O. Box 3065, Stn CSC, Victoria, BC V8W 3V6, Canada;bDepartment of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, Canada; cDepartment of Chemistry, McMasterUniversity, Hamilton, Ontario, L8S 4M1,Canada.

Contents

(i)Additional Figures

(ii)X-ray Crystallographic Details and Data

(i) Additional Figures

Figure SI-1. Solid-state structure of the cation in [Me3Si(pyr)][OTf]. All hydrogen atoms are omitted for clarity.

Figure SI-2. Solid-state structure of one of the two closely related cations in the asymmetric unit of [Me3Si(OPCy3)][OTf]. All hydrogen atoms are omitted for clarity.

Figure SI-3. Solid-state structure of one of the cation in [Me3Si(OpyrMe)][OTf]. All hydrogen atoms are omitted for clarity.

(ii) X-Ray Crystallographic Details and Data

Analysis of single crystals was carried out at either (a) the University of British Columbia ([Me3Si(OpyrMe)][OTf], [Me3Si(pyr)][OTf], [Me3Si(OPPh3)][OTf], [Me3Si(4,4’bipy)SiMe3][OTf]2 and [Me3Si(dmpe)SiMe3][OTf]2), (b) the University of Alberta ((b) [Me3Si(PMe3)][OTf] and [Me3Si(OPCy3)][OTf]) or (c) the MAX Diffraction Facility at McMaster University ((c)[Me3Si(4-dmap)][OTf]). The following procedures were applied:

(a)Crystals were mounted onto a glass fiber and placed into the cold stream of the diffractometer (90 k). Data was collected on a Bruker APEX DUO diffractometer with graphite monochromated Mo-Kα radiation in a series ofφand ω scans in 0.5° oscillations. Data were collected and integrated using the Bruker SAINT1 software package, corrected for absorption effects using the multi-scan technique (SADABS)2, and solved using SHELXT3 and refined against all Fo2 data using SHELXL-2013.4

(b)Crystallographic analysis was carried at 173 K, on a Bruker D8/APEX II CCD using graphite-monochromated Mo Kα radiation (0.71073). Structures were solved using SHELXT4 and refined against all Fo2 data with using SHELXL-97.4

(c) Suitable crystals were selected and mounted in Paratone oil on a MiTeGen loop, then placed in the cold stream of the diffractometer (173 K). Data were collected using 0.5 degree ωand φ scans on a Bruker Apex2 diffractometer using MoKα radiation. Unit cell parameters were determined from three consecutive scans at different orientations. The data were integrated using SAINT1 and then corrected for absorption with SADABS,2 solved with SHELXT4and refined against Fo2 data with SHELXL-97.4

Compound / [Me3Si(4-dmap)][OTf] / [Me3Si(OPCy3)][OTf]
CCDC Number / 1422165 / 1422166
Empirical formula / C11H19F3N2O3SSi / C44H84F6O8P2S2Si2
Formula weight / 344.43 / 1037.35
Temperature/K / 173(2) / 173.15
Crystal system / monoclinic / monoclinic
Space group / P21/c / P21
a/Å / 12.4637(3) / 10.706(3)
b/Å / 10.3455(2) / 18.050(6)
c/Å / 13.1112(3) / 13.911(4)
α/° / 90 / 90
β/° / 104.7280(10) / 97.843(4)
γ/° / 90 / 90
Volume/Å3 / 1635.05(6) / 2663.2(14)
Z / 4 / 2
ρcalcg/cm3 / 1.399 / 1.294
μ/mm1 / 0.311 / 0.273
F(000) / 720.0 / 1112.0
Crystal size/mm3 / 0.383 × 0.309 × 0.268 / 0.509 × 0.316 × 0.229
Radiation / MoKα (λ = 0.71073) / MoKα (λ = 0.71073)
2Θ range for data collection/° / 3.378 to 52.74 / 2.956 to 56.468
Index ranges / -14 ≤ h ≤ 15, -12 ≤ k ≤ 12,
-16 ≤ l ≤ 16 / -14 ≤ h ≤ 14, -23 ≤ k ≤ 23, -18 ≤ l ≤ 18
Reflections collected / 24214 / 40679
Independent reflections / 3360 [Rint= 0.0178, Rsigma= 0.0103] / 12305 [Rint= 0.0637, Rsigma= 0.0627]
Data/restraints/parameters / 3360/0/190 / 12305/1/799
Goodness-of-fit on F2 / 1.038 / 1.022
Final R indexes [I>=2σ (I)] / R1= 0.0508, wR2= 0.1474 / R1= 0.0568, wR2= 0.1455
Final R indexes [all data] / R1= 0.0571, wR2= 0.1554 / R1= 0.0639, wR2= 0.1520
Largest diff. peak/hole / e Å-3 / 0.59/-0.40 / 0.47/-0.63
Flack parameter / N/A / 0.41(4)
Compound / [Me3Si(OPPh3)][OTf] / [Me3Si(OpyrMe)][OTf]
CCDC Number / 1422167 / 1422168
Empirical formula / C22H24F3O4PSSi / C10H16F3NO4SSi
Formula weight / 500.53 / 331.39
Temperature/K / 90(2) / 90
Crystal system / triclinic / orthorhombic
Space group / P-1 / Pnma
a/Å / 7.7677(11) / 25.784(2)
b/Å / 10.7026(15) / 8.7574(8)
c/Å / 14.682(2) / 6.6824(6)
α/° / 86.656(4) / 90
β/° / 76.573(4) / 90
γ/° / 87.464(5) / 90
Volume/Å3 / 1184.6(3) / 1508.9(2)
Z / 2 / 4
ρcalcg/cm3 / 1.403 / 1.459
μ/mm1 / 0.305 / 0.337
F(000) / 520.0 / 688.0
Crystal size/mm3 / 0.29 × 0.28 × 0.18 / Not Recorded
Radiation / MoKα (λ = 0.71073) / MoKα (λ = 0.71073)
2Θ range for data collection/° / 3.814 to 60.37 / 3.16 to 60.18
Index ranges / -10 ≤ h ≤ 10, -15 ≤ k ≤ 15, -20 ≤ l ≤ 20 / -36 ≤ h ≤ 36, -12 ≤ k ≤ 6,
-9 ≤ l ≤ 9
Reflections collected / 26205 / 16362
Independent reflections / 6973 [Rint= 0.0279, Rsigma= 0.0273] / 2357 [Rint= 0.0379, Rsigma= 0.0232]
Data/restraints/parameters / 6973/0/292 / 2357/81/121
Goodness-of-fit on F2 / 1.050 / 1.093
Final R indexes [I>=2σ (I)] / R1= 0.0341, wR2= 0.0879 / R1= 0.0351, wR2= 0.0815
Final R indexes [all data] / R1= 0.0403, wR2= 0.0919 / R1= 0.0445, wR2= 0.0854
Largest diff. peak/hole / e Å-3 / 1.11/-0.47 / 0.59/-0.40
Flack parameter / N/A / N/A
Compound / [Me3Si(PMe3)][OTf] / [Me3Si(pyr)][OTf]
CCDC Number / 1422169 / 1422170
Empirical formula / C7H18F3O3PSSi / C9H14F3NO3SSi
Formula weight / 298.33 / 301.36
Temperature/K / 173(2) / 90(2)
Crystal system / orthorhombic / monoclinic
Space group / Pnma / P21/n
a/Å / 15.010(3) / 8.7157(13)
b/Å / 8.9232(19) / 16.938(3)
c/Å / 10.313(2) / 9.2613(13)
α/° / 90 / 90
β/° / 90 / 95.127(4)
γ/° / 90 / 90
Volume/Å3 / 1381.2(5) / 1361.8(3)
Z / 4 / 4
ρcalcg/cm3 / 1.435 / 1.470
μ/mm1 / 0.462 / 0.360
F(000) / 624.0 / 624.0
Crystal size/mm3 / 0.4 × 0.3 × 0.2 / 0.26 × 0.1 × 0.03
Radiation / MoKα (λ = 0.71073) / MoKα (λ = 0.71073)
2Θ range for data collection/° / 4.792 to 57.002 / 4.81 to 60.148
Index ranges / -20 ≤ h ≤ 19, -11 ≤ k ≤ 10, -13 ≤ l ≤ 13 / -11 ≤ h ≤ 12, -23 ≤ k ≤ 22,
-13 ≤ l ≤ 13
Reflections collected / 9133 / 13683
Independent reflections / 1729 [Rint= 0.1037, Rsigma= 0.0469] / 3988 [Rint= 0.0335, Rsigma= 0.0363]
Data/restraints/parameters / 1729/0/119 / 3988/186/203
Goodness-of-fit on F2 / 1.097 / 1.037
Final R indexes [I>=2σ (I)] / R1= 0.0489, wR2= 0.1232 / R1= 0.0371, wR2= 0.0862
Final R indexes [all data] / R1= 0.0588, wR2= 0.1375 / R1= 0.0508, wR2= 0.0923
Largest diff. peak/hole / e Å-3 / 0.67/-0.34 / 0.58/-0.31
Flack parameter / N/A / N/A
Compound / [Me3Si(4,4’-bipy)SiMe3][OTf]2 / [Me3Si(dmpe)SiMe3][OTf]2
CCDC Number / 1422171 / 1422172
Empirical formula / C20H29F6N3O6S2Si2 / C15H36Cl2F6O6S4Si2
Formula weight / 641.76 / 681.76
Temperature/K / 90(2) / 90(2)
Crystal system / triclinic / orthorhombic
Space group / P-1 / Pnn2
a/Å / 10.3049(11) / 11.3487(9)
b/Å / 10.3842(12) / 15.9959(13)
c/Å / 14.6416(17) / 8.2222(7)
α/° / 83.229(3) / 90
β/° / 74.716(4) / 90
γ/° / 73.068(3) / 90
Volume/Å3 / 1444.4(3) / 1492.6(2)
Z / 2 / 2
ρcalcg/cm3 / 1.476 / 1.517
μ/mm1 / 0.345 / 0.644
F(000) / 664.0 / 708.0
Crystal size/mm3 / 0.39 × 0.21 × 0.05 / 0.53 × 0.50 × 0.43
Radiation / MoKα (λ = 0.71073) / MoKα (λ = 0.71073)
2Θ range for data collection/° / 2.886 to 60.688 / 4.4 to 60.134
Index ranges / -14 ≤ h ≤ 12, -14 ≤ k ≤ 14, -20 ≤ l ≤ 20 / -11 ≤ h ≤ 15, -22 ≤ k ≤ 22,
-11 ≤ l ≤ 11
Reflections collected / 32271 / 18179
Independent reflections / 8572 [Rint= 0.0427, Rsigma= 0.0407] / 4318 [Rint= 0.0229, Rsigma= 0.0189]
Data/restraints/parameters / 8572/0/359 / 4318/1/173
Goodness-of-fit on F2 / 1.020 / 1.055
Final R indexes [I>=2σ (I)] / R1= 0.0356, wR2= 0.0819 / R1= 0.0231, wR2= 0.0670
Final R indexes [all data] / R1= 0.0538, wR2= 0.0895 / R1= 0.0242, wR2= 0.0680
Largest diff. peak/hole / e Å-3 / 0.45/-0.45 / 0.57/-0.35
Flack parameter / N/A / 0.51(7)

References

(1) SAINT: Version 8.34A Bruker AXS Inc., Madison, Wisconsin, USA. (1997-2013).

(2) SADABS: Bruker AXS Inc., Madison, Wisconsin, USA. (1997-2012).

(3) SHELXT: Sheldrick, G. M.; ActaCryst.,2008, A64, 112-122.

(4) SHELX: Sheldrick, G. M.; ActaCryst.,2008, A64, 112-122.

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