Supporting Information for

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1 Supporting Information for Hydrogen-Bridged Digermyl and Germylsilyl Cations N. Kordts, C. Borner, R. Panisch, W. Saak, T. Müller* Contents. 1. Computational Details 2. IR Spectroscopic Results 3. NMR-Spectroscopic Results. 3.1 NMR spectra of compound NMR spectra of compound NMR spectra of compound 7[B(C 6 F 5 ) 4 ] 3.4 NMR spectra of compound 8[B(C 6 F 5 ) 4 ] F NMR spectra of hydrodefluorination reactions. 4. Crystallographic Results for 7[B(C 6 F 5 ) 4 ] 5. References.

2 1. Computational Details. All calculations were done using either the Gaussian03 Rev D.02 or the Gaussian09 Rev. B.01 package of programs. 1 The molecular structures of the cations 2, 7 and 8, were optimized using the nonlocal DFT level of theory, Becke s three-parameter hybrid functional and the LYP correlation (B3LYP 2 ) along with cc-pvtz basis set 3 for all elements. Subsequent frequency calculations at this level of theory verified these structures as minima (zero imaginary frequencies) on the potential energy surface (PES). The Atoms-in-Molecules analysis was done with the AIMALL program 4 applying wavefunctions obtained from single point calculations at the B3LYP/cc-pvtz level of theory. The data are summarized in Tables S-1 (Absolute Energies) and S-3 (Cartesian Coordinates). For calculation of the NMR chemical shifts the GIAO method 5 was used. The M06L functional 6 in connection with the 6-311G(2d,p) basis set was applied on molecular structures optimized at the B3LYP/cc-pvtz level. Computed NMR chemical shieldings were transferred to the chemical shift scale using the NMR chemical shielding of tetramethylsilane (σ(si)(sime 4 ) = 362.1). J-coupling constants were computed at the same level of theory using a modified 6-311G(2d,p) basis set to ensure a better description of the Fermi Contact contribution to coupling constant J. 7 The following atomic units have been used: Elementary charge: 1 au = e = C Charge density ρ : 1 au = e a 0-3 = Cm -3 Laplacian of the charge density 2 ρ : 1 au = e a 0-5 = Cm -5 Energy E : 1 au = e 2 a 0-1 = kj mol -1 Length : 1 au = 1 bohr = pm Energy : 1 au = E h = kj mol -1 Table S1. Calculated absolute energies E, free Gibbs enthalpies G 298 (at 298K, 0.1 MPa) and wavenumbers ν of the asymmetric E-H-E vibration of hydronium ions. Cpd. E [au] G 298 [au] ν as (E-H-E) [cm -1 ] [(Et 3 Si) 2 H] [(Et 3 Ge) 2 H]

3 Table S2. Calculated molecular structures of hydroniumions. Cation 7. B3LYP/cc-pvtz Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

4 Cation 8. B3LYP/cc-pvtz Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

5 Cation 2. B3LYP/cc-pvtz Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z [(Et 3Si) 2H] + B3LYP/cc-pvtz Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

6 [(Et 3Ge) 2H] + B3LYP/cc-pvtz Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

7 2. IR-Spectroscopic Results. For assignment of the IR bands of hydronium ions 7 and 8, their molecular structures were optimized at the B3LYP/cc-pvtz level of theory and subsequent frequency calculations were used to determine the position of the asymmetric E-H-E stretch vibration. To account for anharmonicity effects a scaling factors for the E-H-E vibration was determined from the correlation of the computed data and the experimental results for cations 2, 7, 8, [Et 3 SiHSiEt 3 ] + and [Et 3 GeHGeEt 3 ] + 8 From this correlation a scaling factor of was determined (see Figure S1). The global scaling factor for wavenumbers of vibrations computed at B3LYP/cc-pvtz was previously determined to be Figure S1. Correlation between the experimental wavenumber of the ν as (E-H-E) vibration (E= Si, Ge) and computed data and calculated data obtained at B3LYP/cc-pvtz. The line of best fit (black) is given by the following equation: ν calc = ν exp. Figure S2. Comparison between experimental (neat, ATR) and computed IR spectra (B3LYP/cc-pvtz, line width: 4 cm -1 ) of hydronium borates 7[B(C 6 F 5 ) 4 ] (a), 8[B(C 6 F 5 ) 4 ] (b) and 2[B(C 6 F 5 ) 4 ] (c); (blue trace: experimental data, red trace: computed data for [B(C 6 F 5 ) 4 ] - ; black trace: computed data for cations 7, 8 and 2).

8 3. NMR-Spectroscopic Results. 3.1 NMR spectra of compound 10 Figure S MHz 1 H NMR spectrum of 10 in C 6 D 6 at 305 K; δ 1 H = ; #: C 6 D 5 H; +: impurity. Figure S MHz 13 C{ 1 H} NMR spectrum of 10 in C 6 D 6 at 305 K; δ 13 C = 145-0; #: C 6 D 5 H; +: impurity; unknown substance at δ 13 C = 15.1, 26.7, 29.1.

9 3.2 NMR spectra of compound 12 Figure S MHz 1 H NMR spectrum of 12 in C 6 D 6 at 305 K; δ 1 H = ; #: δ 1 H(C 6 D 6 ) = 7.20; o: signals of 1-Dimethylsilylnaphthalene. Figure S MHz 13 C{ 1 H} NMR spectrum of 12 in C 6 D 6 at 305 K; δ 13 C = 150-(-5); #: δ 13 C(C 6 D 6 ) = 128.0; o: signals of 1-Dimethylsilylnaphthalene.

10 Figure S7. 99 MHz 29 Si{ 1 H}-INEPT NMR spectrum of 12 in C 6 D 6 at 305 K; δ 29 Si = -8-(-31); o: signals of 1-Dimethylsilylnaphthalene.

11 3.3 NMR spectra of compound 7[B(C 6 F 5 ) 4 ] Figure S MHz 1 H NMR spectrum of 7[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 1 H = ; #: C 6 D 5 H; +: decomposition. Figure S MHz 13 C{ 1 H} NMR spectrum of 7[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 13 C = ; #: C 6 D 5 H; o: signals of [B(C 6 F 5 ) 4 ] -.

12 Figure S10. Part of the 500 MHz 1 H/ 1 H COSY NMR spectrum of 7[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 1 H (f2) = ; δ 1 H (f1) = Figure S11. Part of the 1 H 13 C HMBC NMR spectrum of 7[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 1 H (f2) = ; δ 13 C (f2) =

13 3.4 NMR spectra of compound 8[B(C 6 F 5 ) 4 ] Figure S MHz 1 H NMR spectrum of 8[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 1 H = ; #: C 6 D 5 H; +: impurity. Figure S MHz 13 C{ 1 H} NMR spectrum of 8[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 13 C = 151- (-0.5); #: C 6 D 5 H; o: signals of [B(C 6 F 5 ) 4 ] -.

14 Figure S MHz 29 Si{ 1 H} INEPT NMR spectrum of 8[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 29 Si = 80-(-50); +: impurity; reference against external Si(CH 3 ) 4. Insert: 99 MHz 29 Si INEPT NMR spectrum of 2[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 29 Si = Figure S15. Part of the 500 MHz 1 H / 1 H COSY NMR spectrum of 8[B(C 6 F 5 ) 4 ] in C 6 D 6 at 305 K; δ 1 H (f2) = ; δ 1 H(f1) =

15 4. Crystallographic Results for 7[B(C 6 F 5 ) 4 ] Empirical formula C50 H43 B F20 Ge2 Formula weight Temperature 120(2) K Wavelength Å Crystal system Monoclinic Space group Cc Unit cell dimensions a = (8) Å α= 90. b = (6) Å β= (2). c = (7) Å γ = 90. Volume (3) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 2368 Crystal size 0.47 x 0.26 x 0.19 mm 3 Theta range for data collection 1.91 to Index ranges -25<=h<=27, -20<=k<=21, -25<=l<=24 Reflections collected Independent reflections (R(int) = ) Observed reflections (>2sigma(I)) Completeness to theta = % Absorption correction Numerical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 2 / 665 Goodness-of-fit on F Final R indices (I>2sigma(I)) R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.007(4) Largest diff. peak and hole and e.å -3

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