· 3 1.2. Syntheses 1.2.1. General Procedure: Preparation of Bis(catecholato)silanes – Si(catX) 2( 2 CH3CN) O Si O O O 1 eq. HSiCl 3 OH OH Y X Y X X Y X Y X Y X Y N N CH 3 CN 40
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1
Supporting Information for:
Bis(catecholato)silanes: assessment, rationale and increase of silicon’s Lewis superacidity
1.2.1. General Procedure: Preparation of Bis(catecholato)silanes – Si(catX)2(●2 CH3CN ...........3
1.2.2. General Procedure: Assessment of Lewis Acidity by the Gutmann-Beckett Method – Preparation of Et3PO-Adducts .........................................................................................................5
1.2.3. General Procedure: Preparation of Monofluoride Adducts of Bis(catecholato)silanes ..9
1.2.4. General Procedure: Preparation of Monochloride Adducts of Bis(catecholato)silanes11
1.2.5. General Procedure: Catalytic Hydrodefluorination Reaction of 1-Adamantylfluoride..13
1.2.6. General Procedure: Assessment of Relative Solution Phase Fluoride and Chloride Ion Affinities (FIAsol and CIAsol) – Fluoride- and Chloride-Exchange Reactions ....................................14
1.2.7. Scrambling Experiments between two Fluoride Adducts..............................................19
1.2.8. General Procedure: Chloride-Abstraction from Trityl Chloride .....................................20
2. Definition of Berry coordinate and Topography Parameter (TP) ..................................................21
Due to different stereoisomers of the preferred tbp-confirmation (see Figure S5), three 19F-NMR
resonances are observed. A dynamic equilibrium between the two trans-diastereomeres via Berry-
pseudorotation causes signal broadening. The sharp mid signal should stem from the cis-tbp
stereoisomer, which is separated from the trans isomers through a larger energetic barrier. The same
dynamic effects caused severe signal broadening in the 13C-NMR spectra, hampering peak
identification.
10
Figure S5: 19F-NMR spectrum of [K@18-crown-6][F-Si(cattBu)2]. Formation of trans-diastereomers [K@18-crown-6][F-Si(cattBu)2]-A and [K@18-crown-6][F-Si(cattBu)2]-B, as well as 1.9 % of a cis-tbp isomer (δ = −133.7 ppm).
1.2.5. General Procedure: Catalytic Hydrodefluorination Reaction of 1-Adamantylfluoride
F2 eq. Et3SiH
3 mol% Si(catx)275 °C, CD3CN
X = F, Cl, Br
1-Adamantylfluoride (1 eq., 20.0 mg, 130 µmol), Et3SiH (2 eq., 30.2 mg, 260 µmol) and 3 mol% of
Si(catX)2 were mixed in 0.5 ml CD3CN. The sample was inserted in the preheated NMR machine at 75 °C
and NMR spectra were recorded at fixed time intervals. The conversion was determined by 19F-NMR
integration against C6F6 (43 mM) as internal standard (see Figure S6).
Figure S6: 19F-NMR spectra of Si(catBr)2 catalyzed hydrodefluorination of 1-adamantylfluoride recorded
between t = 0 and t = 240 min. F-Ad (δ 19F = –128.0 ppm) depicts the resonance of the decreasing educt while the peak at –175.4 ppm corresponds to the increasing side product F-SiEt3.
14
1.2.6. General Procedure: Assessment of Relative Solution Phase Fluoride and Chloride Ion
Affinities (FIAsol and CIAsol) – Fluoride- and Chloride-Exchange Reactions
OSi
O
O
OZ
orK+@18-crown-6
OSi
O
O
OY
Y
Y
Y
Z
XX
XXX
X
XX
Y
Y Y
Y
X/Y = H, F, Cl, Br, 3,5-tBu
Ph3P=N+=PPh3 Z = F or Clor
K+@18-crown-6
Ph3P=N+=PPh3
Si(catY)2 Si(catX)2
[K@18-crown-6][F-Si(catX)2] or [PPN][Cl-Si(catX)2] (1 eq., 25.0 µmol) was dissolved in 0.5 ml CD2Cl2 and
Si(catY)2 (1 eq., 25.0 µmol) was added. The formed suspension was mixed until equilibrium was
reached (min 36 h, up to 5d at 40°C). The reaction was monitored by 1H/13C/19F/29Si-NMR spectroscopy.
Table for FIAsol: see main text.
Figure S7a: 19F NMR spectra of all [F-Si(catX)2]– species (X = H, 3,5-tBu, F, Cl, Br) at room temp. in CD2Cl2.
15
Figure S7b: 19F NMR spectra of [F-Si(catX)2]– + Si(catY)2 for X/Y = H, tBu (0.05 M, CD2Cl2, room temp.),
calibrated on the [F-Si(catX)2]– signals (top and bottom).
Figure S7c: 19F NMR spectra of [F-Si(catX)2]– + Si(catY)2 for X/Y = H, F (0.05 M, CD2Cl2, room temp.),
calibrated on the [F-Si(catX)2]– signals (top and bottom).
16
Figure S7d: 19F NMR spectra of [F-Si(catX)2]– + Si(catY)2 for X/Y = tBu, F (0.05 M, CD2Cl2, room temp.),
calibrated on the [F-Si(catX)2]– signals (top and bottom).
Figure S7e: 19F NMR spectra of [F-Si(catX)2]– + Si(catY)2 for X/Y = F, Cl (0.05 M, CD2Cl2, room temp.),
calibrated on the [F-Si(catX)2]– signals (top and bottom).
17
Figure S7f: 19F NMR spectra of [F-Si(catX)2]– + Si(catY)2 for X/Y = F, Br (0.05 M, CD2Cl2, room temp.),
calibrated on the [F-Si(catX)2]– signals (top and bottom).
Figure S7g: 19F NMR spectra of [F-Si(catX)2]– + Si(catY)2 for X/Y = Cl, Br (0.05 M, CD2Cl2, room temp.),
calibrated on the [F-Si(catX)2]– signals (top and bottom).
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[Cl-Si(catX)2]- + Si(catY)2
Chloride abstraction observed?
Monitored by rel. CIAsol
X = H, Y = tBu no 1H/13C-NMR
X = tBu, Y = H yes 1H/13C/29Si-NMRH > tBu
X = H, Y = F yes 19F/29Si-NMR
X = F, Y = H no 19F/29Si-NMRF > H
X = tBu, Y = F yes 19F/29Si-NMR
X = F, Y = tBu no 19F/29Si-NMRF > tBu
X = F, Y = Cl yes 1H/13C/29Si-NMR
X = Cl, Y = F no 13C-NMRCl > F
X = F, Y = Br yes 13C/29Si-NMR
X = Br, Y = F no 13C/29Si-NMRBr > F
X = Br, Y = Cl no 13C/29Si-NMR Br > Cl
X = H, Y = Cl yes 13C/29Si-NMR Cl > H
X = tBu, Y = Cl yes 13C/29Si-NMR Cl > tBu
0.05 M of [PPN][Cl-Si(catX)2] and 0.05 M Si(catY)2 in CD2Cl2, room temp., min. 36 h equilibration time, for Y = Cl and Br, the CH3CN adducts were used.
Table S2: Relative solution phase chloride ion affinity: Overview of performed chloride abstraction experiments and used detection methods, the last column gives the relative solution phase chloride ion affinities.
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1.2.7. Scrambling Experiments between two Fluoride Adducts
OSi
O
O
OF
K+@18-crown-6
OSi
O
O
OY
Y
Y
Y
F
K+@18-crown-6
OSi
O
O
OF
K+@18-crown-6
Y
YXX
XXX
X
XX X
X
XX Y
Y
Y
Y Y
Y
X/Y = H, F, Cl, Br, 3,5-tBu
Equimolar amounts of two different [K@18-crown-6][F-Si(catX/Y)2] were dissolved in 0.5 ml CD2Cl2.
Formation of new heteroleptic species was monitored by 19F and 29Si-NMR spectroscopy as well as X-
ray diffraction (for X = F, Y = Br) and ESI-HRMS (for X = H, Y = F; X = F, Y = Cl; and X = Cl, Y = Br).
[K@18-crown-6][Si(catH)(cattBu)2]: 19F-NMR: (376 MHz, CD2Cl2): δ = −133.7 (s, 1F), −133.8 (s, 1F). 29Si-NMR (79 MHz, CD2Cl2): δ = −104.8 (d, 1JSi,F = 190.8 Hz). No additional signal could be observed in
the 29Si-NMR spectrum because both educts have the same shift and coupling constant.
1.2.8. General Procedure: Chloride-Abstraction from Trityl Chloride
OSi
O
O
O
YX
YX
XY
XY
OSi
O
O
O
YX
YX
XY
XY
Cl
CD2Cl2X = H, F, Cl, Br, tBuY = H, F, Cl, Br
Tritylchloride
Ph
PhPh
To a solution of trityl chloride (1 eq., 2.90 mg, 10.4 µmol) in 0.5 ml CD2Cl2 1 eq. Si(catX)2 was added. For
X = H, tBu no considerable reaction took place, for X = F, Cl, Br the solution turned yellow, indicating
the formation of the tritylium cation along with the corresponding chloridosilicate [CPh3][Cl-Si(catX)2]
in a ratio given in table 5 in the main part. Conversion was monitored by integration of 1H-NMR spectra
(see Figure S8). Signs of degradation of the trityl cations were observable after heating the mixtures
for > 24 at 50 °C. The obtained equilibrium data was obtained after only 2 h, wherein this
decomposition was negligible/invisible.
NMR data for the chlorosilicates are given in chapter 1.2.5.
Figure S8: 1H-NMR spectrum of the mixture of Si(catCl)2●2 CH3CN and tritylchloride after 1.5 h at 50 °C. The three left signals correspond to the tritylium cation whilst the multiplett on the right belongs to unreacted tritylchloride.
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2. Definition of Berry coordinate and Topography Parameter (TP)
Considering the geometry of pentavalent compounds, there are two main coordination forms: the
more common trigonal-bipyramidal (tbp) and less common square planar (sp) form. There is a change
with only a small energy barrier from tbp to a sp geometry.
The distortion takes place along the Berry coordinate (see Figure S9). Couzijn et. al gives a simple
quantitative description of this effect by using a topology parameter (TP).[3] The obtained value allows
a rough estimation of the distortion along the Berry coordinate. The TP ranges from 1 = ideal tbp to
0 = ideal sp. The largest angle is defined as Θax. The three remaining atoms lie in the plane of the
trigonal pyramid, the largest angle therein is defined as Θeq. The Berry coordinate is defined by the axis
of the remaining atom and the center.
Berry coordinate
Figure S9: Formula and schematic depiction for the computation of the topology parameter.
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3. Computational Details
3.1. Geometry optimization and single point energies for FIA/CIA computations
Geometry optimizations and single point energy calculations have been performed with ORCA 4.0.1.[4]
The RI approximation[5] for the Coulomb integrals was used in all cases (RIJCOSX), with application of
corresponding auxiliary basis sets.[6] Previous benchmark studies on the ideal method for geometry
optimization revealed the PW6B95[7] including Grimme’s semi-empirical dispersion correction[8] with
Becke-Johnson damping function[9] (D3(BJ) and the def2-TZVPP[10] basis set as ideal to reproduce the
experimental solid-state structural parameters. All calculated geometries have been confirmed as
energetic minima on the potential energy surface by analytical calculation of harmonic frequencies at
the BP86-D3(BJ)/def2-SVP level. Enthalpies at 298 K have been calculated with the same level of theory
by using the rigid-rotor harmonic oscillator (RRHO) approximation,[11] as implemented in ORCA. The
final single point electronic energies for the evaluation of FIA/CIA were calculated with the highly
accurate and linear scaling version of domain based localized pair natural orbitals based coupled
cluster theory (DLPNO-CCSD(T)), as implemented in ORCA 4.0.[12] It has been shown that the DLPNO-
CCSD(T) method reproduces experimentally obtained bond energies within an accuracy of < 1 kcal mol-
1.[13] Benchmark calculations with TightPNO vs NormalPNO settings revealed a change of energies by <
1 kcal/mol-1, thus NormalPNO settings and the default thresholds were used throughout these studies.
Dunning’s augmented correlation consistent aug-cc-pVQZ basis set and matching auxiliary basis sets
were used for all DLPNO-CCSD(T) single point energies. As it can be expected with this basis set size,
no extrapolation techniques or BSSE corrections are required for an accurate description.[14]
The final FIA/CIA reaction enthalpies were calculated according to the scheme proposed by Krossing,[15]
using the therein given G3 anchor points and isodesmic reactions. Due to heavy linear dependencies
in the FIA calculation for Si(OPh)4 with DLPNO-CCSD(T)/aug-cc-pVQZ, the smaller cc-pVQZ basis set
(without augmented functions) had to be used exclusively in this case. Based on comparative
computations of the FIA with cc-pVQZ vs. aug-cc-pVQZ (SiH4, Si(OMe)4, Si(cat)2), an amount of
6 kJ mol-1 was added to the cc-pVQZ value of Si(OPh)4. Table S3 lists all relevant data for the FIA and
CIA calculation. The FIA of other Lewis acids in Figure 5 in the main text have been computed at the
same level of theory and details will be reported as part of a larger FIA collection in close future.
The corresponding solvation free enthalpies were obtained from COSMO-RS[16] calculations as
implemented in the ADF program package,[17] based on BP86-D3/TZP[18] single point energy
calculations for the solute-solvent interaction (Table S3d). The final solvation corrected enthalpies
were obtained by combining the solvation energies for X-, the respective Lewis acid and the fluoride
adduct with the DLPNO-CCSD(T)/aug-cc-pVQZ vacuum enthalpies.
Table S3c: Computation of FIAs at the DLPNO-CCSD(T)/aug-cc-pVQZ level of theory (including thermal and ZPE correction from BP86). athe cc-pVQZ basis set was used and extrapolated to aug-cc-pVQZ energy (+6 kJ mol, see text above)
26
Compound free Energy of solvation (COSMO-RS, kJ/mol)
[F-Si(OPh)4]- -213.9 -63337960.4 126.7 Cl- -270.0Table S3d: Combination of energies of solvation (COSMO-RS, in CH2Cl2) with FIA and CIA at the DLPNO-CCSD(T)/aug-cc-pVQZ level of theory.
27
3.2. Discussion of the influence of CH3CN for Si(catCl)2
The association equilibria of CH3CN with Si(catCl)2 were computed at the PW6B95-D3(BJ)/def2-TZVPP
level of theory. Enthalpies and entropies at 298 K have been calculated at the BP86-D3(BJ)/def2-SVP
level by using the rigid-rotor harmonic oscillator (RRHO) approximation,[11] as implemented in ORCA.
Figure S10: Thermodynamics of the dissociation of CH3CN from Si(catCl)2●2 CH3CN computed at
PW6B95-D3(BJ)/def2-TZVPP, all values in kJ mol-1.
It can be seen, that the spontaneous dissociation of two units of CH3CN from Si(catCl)2●2 CH3CN is indeed
favorable, due to entropy gain (endothermic but exergonic). This makes the overall discussion based
on the free acids as plausible. The FIA (enthalpy!) of the CH3CN bis-adduct is attenuated by the loss of
bond energy of Si-NCCH3, but the FIA of the mono-adduct is actually even larger as the FIA for the free
Lewis acid.
3.3. 29Si-NMR shift calculation
29Si-NMR chemical shifts of the chlorosilicates [Cl-Si(catX)2]- were calculated based on the PW6B95-
D3(BJ)/def2-TZVPP structures using the respective modules[19] in the ADF program package, with the
PBE0 hybrid functional[20] and a triple-ζ Slater type basis set (TZ2P)[18], in which relativistic spin orbit
contributions to the magnetic shielding constants were treated by the two-component zero order
regular approximation (SO-ZORA).[21] Solvation (CH2Cl2) was modeled with COSMO[22] as implemented
in ADF.[23] NMR chemical shifts are given relative to TMS (0 ppm), calculated at the same level of theory.
Identification code ms19fEmpirical formula C19H17Br8Cl2O5PSiFormula weight 1094.56Temperature/K 120Crystal system triclinicSpace group P-1a/Å 11.061(2)b/Å 12.978(3)c/Å 22.591(5)α/° 86.42(3)β/° 79.44(3)γ/° 67.26(3)Volume/Å3 2940.2(12)Z 4ρcalc g/cm3 2.473μ/mm-1 11.219F(000) 2056.0Crystal size/mm3 0.5 × 0.4 × 0.35Radiation MoKα (λ = 0.71073)2Θ range for data collection/° 3.402 to 57.998
Index ranges -14 ≤ h ≤ 15, -17 ≤ k ≤ 17, -30 ≤ l ≤ 30
Reflections collected 29045Independent reflections 15632 [Rint = 0.0630, Rsigma = 0.1036]Data/restraints/parameters 15632/0/655Goodness-of-fit on F2 0.958Final R indexes [I>=2σ (I)] R1 = 0.0437, wR2 = 0.0672Final R indexes [all data] R1 = 0.1004, wR2 = 0.0784Largest diff. peak/hole / e Å-3 0.93/-1.09Multi-scan absorption correction (Bruker Sadabs) was used. The unordinary displacement parameter of C11 could not be resolved, and might stem from phase transition upon cooling of the crystal.
33
Et3PO-Si(catF)2
Identification code ms93_P21Empirical formula C18H15O5F8SiPFormula weight 522.36Temperature/K 120Crystal system monoclinicSpace group P21/ca/Å 21.898(4)b/Å 12.467(3)c/Å 14.654(3)α/° 90β/° 91.49(3)γ/° 90Volume/Å3 3999.2(14)Z 8ρcalc g/cm3 1.735μ/mm-1 0.302F(000) 2112.0Crystal size/mm3 0.5 × 0.5 × 0.4Radiation MoKα (λ = 0.71073)2Θ range for data collection/° 3.76 to 58
Index ranges -29 ≤ h ≤ 29, -16 ≤ k ≤ 17, -19 ≤ l ≤ 19
Goodness-of-fit on F2 1.074Final R indexes [I>=2σ (I)] R1 = 0.0634, wR2 = 0.1574Final R indexes [all data] R1 = 0.1055, wR2 = 0.1769Largest diff. peak/hole / e Å-3 0.74/-0.40Disorder in CH2 and CH3 groups and C6F4 ring.[K@18-crown-6][F-Si(catF)2], polymorph A
Identification code ms83_P1Empirical formula C24H24F9KO10SiFormula weight 710.62Temperature/K 120Crystal system triclinicSpace group P-1a/Å 9.3030(19)b/Å 10.781(2)c/Å 15.544(3)α/° 77.14(3)β/° 77.77(3)γ/° 69.26(3)Volume/Å3 1406.2(6)Z 2ρcalc g/cm3 1.678μ/mm-1 0.347F(000) 724.0Crystal size/mm3 0.6 × 0.55 × 0.4Radiation MoKα (λ = 0.71073)2Θ range for data collection/° 4.094 to 60.246
Index ranges -13 ≤ h ≤ 13, -14 ≤ k ≤ 15, -21 ≤ l ≤ 21
Data/restraints/parameters 8277/0/409Goodness-of-fit on F2 1.007Final R indexes [I>=2σ (I)] R1 = 0.0664, wR2 = 0.1191Final R indexes [all data] R1 = 0.1758, wR2 = 0.1485Largest diff. peak/hole / e Å-3 0.95/-0.86Et2O-Si(catBr)2-OEt2
Identification code ms125aEmpirical formula C20H20Br8O6SiFormula weight 1023.73Temperature/K 120Crystal system MonoclinicSpace group P21/ca/Å 8.6390(17)b/Å 9.5980(19)c/Å 17.384(4)α/° 90β/° 93.00(3)γ/° 90Volume/Å3 1439.5(5)Z 2ρcalc g/cm3 2.362μ/mm-1 11.219F(000) 964.0Crystal size/mm3 0.45 × 0.45 × 0.4Radiation MoKα (λ = 0.71073)2Θ range for data collection/° 4.692 to 56Index ranges -9 ≤ h ≤ 11, -11 ≤ k ≤ 12, -22 ≤ l ≤ 22Reflections collected 11000Independent reflections 3415 [Rint = 0.0635, Rsigma = 0.0861]
45
Data/restraints/parameters 3415/0/162Goodness-of-fit on F2 0.993Final R indexes [I>=2σ (I)] R1 = 0.0404, wR2 = 0.0618Final R indexes [all data] R1 = 0.0814, wR2 = 0.0709Largest diff. peak/hole / e Å-3 0.79/-0.895. NMR Spectra
13C-NMR (100 MHz, DMF) of Si(cattBu)2(DMF).
13C-NMR (100 MHz, DMF) of Si(catCl)2(DMF).
46
13C-NMR (100 MHz, DMF) of Si(catBr)2(DMF).
1H-NMR (400 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catH)2].
13C-NMR (100 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catH)2].
47
19F-NMR (376 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catH)2].
29Si-NMR (79 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catH)2].
1H-NMR (400 MHz, CD2Cl2) of [K@18-crown-6][F-Si(cattBu)2].
48
49
13C-NMR (100 MHz, CD2Cl2) of [K@18-crown-6][F-Si(cattBu)2]. Due to dynamic effects between different stereoisomers of the preferred tbp-confirmation (see Figure S5), severe signal broadening occurred, hampering peak identification.
19F-NMR (376 MHz, CD2Cl2) of [K@18-crown-6][F-Si(cattBu)2].
50
29Si-NMR (79 MHz, CD2Cl2) of [K@18-crown-6][F-Si(cattBu)2].
1H-NMR (400 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catF)2].
13C-NMR (100 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catF)2].
51
19F-NMR (376 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catF)2].
29Si-NMR (79 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catF)2].
1H-NMR (400 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catCl)2].
52
13C-NMR (100 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catCl)2].
19F-NMR (376 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catCl)2].
29Si-NMR (79 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catCl)2].
53
1H-NMR (400 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catBr)2].
13C-NMR (100 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catBr)2].
19F-NMR (376 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catBr)2].
54
29Si-NMR (79 MHz, CD2Cl2) of [K@18-crown-6][F-Si(catBr)2].
1H-NMR (400 MHz, CD2Cl2) of [PPN][Cl-Si(catH)2].
55
13C-NMR (100 MHz, CD2Cl2) of [PPN][Cl-Si(catH)2].
29Si-NMR (79 MHz, CD2Cl2) of [PPN][Cl-Si(catH)2].
31P-NMR (162 MHz, CD2Cl2) of [PPN][Cl-Si(catH)2].
56
1H-NMR (400 MHz, CD2Cl2) of [PPN][Cl-Si(cattBu)2].
13C-NMR (100 MHz, CD2Cl2) of [PPN][Cl-Si(cattBu)2].
29Si-NMR (79 MHz, CD2Cl2) of [PPN][Cl-Si(cattBu)2].
57
31P-NMR (162 MHz, CD2Cl2) of [PPN][Cl-Si(cattBu)2].
1H-NMR (400 MHz, CD2Cl2) of [PPN][Cl-Si(catF)2].
58
13C-NMR (100 MHz, CD2Cl2) of [PPN][Cl-Si(catF)2]. Assignement of cat-signals was not possible due to the higher order multiplets of carbon caused by fluorine coupling
19F-NMR (376 MHz, CD2Cl2) of [PPN][Cl-Si(catF)2].
59
29Si-NMR (79 MHz, CD2Cl2) of [PPN][Cl-Si(catF)2].
31P-NMR (162 MHz, CD2Cl2) of [PPN][Cl-Si(catF)2].
1H-NMR (400 MHz, CD2Cl2) of [PPN][Cl-Si(catCl)2].
60
13C-NMR (100 MHz, CD2Cl2) of [PPN][Cl-Si(catCl)2].
29Si-NMR (79 MHz, CD2Cl2) of [PPN][Cl-Si(catCl)2].
31P-NMR (162 MHz, CD2Cl2) of [PPN][Cl-Si(catCl)2].
61
1H-NMR (400 MHz, CD2Cl2) of [PPN][Cl-Si(catBr)2].
13C-NMR (100 MHz, CD2Cl2) of [PPN][Cl-Si(catBr)2].
62
29Si-NMR (79 MHz, CD2Cl2) of [PPN][Cl-Si(catBr)2]. The signal at –109.9 ppm belongs to a so far unidentified second species, in which another donor coordinates at the [Cl-Si(catBr)2]- moiety.
31P-NMR (162 MHz, CD2Cl2) of [PPN][Cl-Si(catBr)2].
63
References
[1] a) H. R. Allcock, T. A. Nugent, L. A. Smeltz, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry 1972, 2, 97-104; b) A. K. Chekalov, A. I. Prokof'ev, N. N. Bubnov, S. P. Solodovnikov, A. A. Zhdanov, M. I. Kabachnik, Bull. Acad. Sci. USSR, Div. Chem. Sci. 1981, 30, 2064-2071; c) E. Hey-Hawkins, U. Dettlaff-Weglikowska, D. Thiery, H. G. von Schnering, Polyhedron 1992, 11, 1789-1794; d) A. L. Liberman-Martin, R. G. Bergman, T. D. Tilley, J. Am. Chem. Soc. 2015, 137, 5328-5331.
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