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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2015 Supporting Information Are intramolecular frustrated Lewis pairs also intramolecular catalysts? A theoretical study on H 2 activation. Lei Liu Zeonjuk, a Petko St. Petkov, a Thomas Heine, a Gerd-Volker Röschenthaler, a Johannes Eicher, b Nina Vankova, *a a Department of Physics & Earth Sciences, Jacobs University Bremen, Campus Ring 1, Bremen, Germany b Solvay Fluor GmbH, Hans-Böckler-Allee 20, Hannover, Germany 1

2 Tables Table S1. Relative potential energies ( E) calculated at different levels of theory for the three conformations of Mes 2 PCH 2 CH 2 B(C 6 F 5 ) 2, 1. All energy values are in kj mol 1, and are referred to the energy of the closed form of 1). Level of theory 1 gauche-1 trans-1 B97D/6-31G* (gas-phase geometry) SCS-MP2/cc-pVTZ//B97D/6-31G* (gas-phase geometry + solvent corrections) ωb97xd/6-31+g** (solvent-phase geometry) SCS-MP2/cc-pVTZ//B97D/6-31+G** (solvent-phase geometry) Table S2. Relative potential energies ( E) calculated at different levels of theory for the stationary points along the reaction coordinate of an intramolecular H 2 activation by 1. All energy values are in kj mol 1, and are referred to the total energy of the closed conformer and an isolated H 2 molecule (1 + H 2 ). Level of theory gauche-1 + H 2 TS1 gauche-pd1 trans-pd1 B97D/6-31G* (gas phase) B97D/6-31+G** (gas phase) B97D/6-31G* (single point solvent phase) B97D/6-31+G** (solvent phase) SCS-MP2/cc-pVTZ//B97D/6-31G* (gas phase) SCS-MP2/cc-pVTZ//B97D/6-31G* (single point solvent phase) SCS-MP2/cc-pVTZ//B97D/6-31+G** (solvent phase) Table S3. Relative Gibbs energies ( G) calculated at different levels of theory for the stationary points along the reaction coordinate of an intramolecular H 2 activation by 1. All energy values are in kj mol 1, and are referred to the total energy of the closed conformer and an isolated H 2 molecule (1 + H 2 ). Level of theory gauche-1 + H 2 TS1 gauche-pd1 trans-pd1 B97D/6-31G* (gas phase) B97D/6-31+G** (gas phase) B97D/6-31G* (single point solvent phase) B97D/6-31+G** (solvent phase) SCS-MP2/cc-pVTZ//B97D/6-31G* (gas phase) SCS-MP2/cc-pVTZ//B97D/6-31G* (single point solvent phase) SCS-MP2/cc-pVTZ//B97D/6-31+G** (solvent phase)

3 Table S4. Relative potential energies ( E) calculated at three different density functionals, at the MP2 and at the SCS-MP2 levels of theory for the stationary points along the reaction coordinate of an intramolecular H 2 activation by 1. All energy values are in kj mol 1, and are referred to the total energy of the open gauche conformer and an isolated H 2 molecule (gauche-1 + H 2 ). The tabulated values are derived from gas-phase single point calculations on geometries optimized at the B97D/6-31G* level of theory, without inclusion of the ZPE corrections. Level of theory TS1a gauche-pd1 trans-pd1 B97D/6-31G* MP2/cc-pVTZ SCS-MP2/cc-pVTZ B97D3/6-31G* M062X/6-31G* Table S5. Relative potential energies ( E) calculated at three different density functionals, at the MP2 and at the SCS-MP2 levels of theory for the stationary points along the reaction coordinate of an intramolecular H 2 activation by 2. All energy values are in kj mol 1, and are referred to the total energy of the open cis conformer and an isolated H 2 molecule (cis-1 + H 2 ). The tabulated values are derived from gas-phase single point calculations on geometries optimized at the B97D/6-31G* level of theory, without inclusion of the ZPE corrections. Level of theory TS2 gauche-pd2 B97D/6-31G* MP2/cc-pVTZ SCS-MP2/cc-pVTZ B97D3/6-31G* M062X/6-31G* Table S6. Relative potential energies ( E) calculated at three different density functionals, at the MP2 and at the SCS-MP2 levels of theory for the stationary points along the reaction coordinate of an intermolecular H 2 activation by 1. All energy values are in kj mol 1, and are referred to the total energy of the open gauche conformer and an isolated H 2 molecule (gauche-1 + H 2 ). The tabulated values are derived from gas-phase single point calculations on geometries optimized at the B97D/6-31G* level of theory, without inclusion of the ZPE corrections. Level of theory trans-1 dimer-1 TS1b dimer- PD1 TS1c dimer- PD1' B97D/6-31G* MP2/cc-pVTZ SCS-MP2/cc-pVTZ B97D3/6-31G* M062X/6-31G*

4 Table S7. Selected distances and bond lengths (in Å), and natural charges (in units of elementary charge) of the P, B and H atoms from H 2, as obtained for the stationary points along the reaction path of the intramolecular mechanism of the H 2 activation by 1. TS and PD denote transition state and hydrogenated product, respectively. H P and H B denote the hydrogen atoms that are close or bound to phosphorus and boron, respectively. The equilibrium H H bond is calculated as d HH = 0.74 Å. All parameters are derived from B97D/6-31G(d,p) calculations in gas phase. Stationary points along the reaction coordinate Distances and bond lengths Natural charges d PB, Å d PH, Å d BH, Å d HH, Å P B H P H B e +0.39e gauche e +0.87e TS1a e +0.13e 0.00e gauche-pd e +0.11e +0.06e -0.02e trans-pd e +0.13e +0.05e 0.01e Table S8. Selected distances and bond lengths (in Å), and natural charges (in units of elementary charge) of the P, B and H atoms from H 2, as obtained for the stationary points along the reaction path of the intramolecular mechanism of the H 2 activation by 1. TS and PD denote transition state and hydrogenated product, respectively. H P and H B denote the hydrogen atoms that are close or bound to phosphorus and boron, respectively. The equilibrium H H bond is calculated as d HH = 0.74 Å. All parameters are derived from B97D/6-31G(d,p) calculations in solvent phase (toluene, ε = ). Stationary points along the reaction coordinate Distances and bond lengths Natural charges d PB, Å d PH, Å d BH, Å d HH, Å P B H P H B e +0.42e gauche e +0.87e TS1a e +0.63e +0.13e 0.00e gauche-pd e +0.11e +0.06e -0.01e trans-pd e +0.13e +0.06e 0.00e Table S9. Potential energy of dimerization without (ΔE) and with (CP-ΔE) the counterpoise correction (CP) included, as calculated for compound 1. The values (in kj mol 1 ) are obtained at the SCS-MP2/cc-pVTZ//B97D/6-31G(d) level of theory. Dimerization reaction ΔE CP CP-ΔE 2trans-1 dimer trans-PD1 dimer-pd1'

5 Table S10. Relative potential energies ( E, 0K) and Gibbs energies ( G, K) calculated for the three conformations of Mes 2 PCHPhCH 2 B(C 6 F 5 ) 2, 2. All energy values are in kj mol 1, calculated at the SCS-MP2/cc-pVTZ//B97D/6-31G(d) level of theory (gas-phase optimization with single point corrections for toluene), and are referred to the energy of the closed form of 2. Relative energy 2 cis-2 trans-2 E sol 0.0 G sol Table S11. Selected distances and bond lengths (in Å), as obtained for the stationary points along the reaction path of the intramolecular mechanism of the H 2 activation by 2. TS and PD denote transition state and hydrogenated product, respectively. The equilibrium H H bond is calculated as d HH = 0.74 Å. All parameters are derived from B97D/6-31G(d) calculations in gas phase. Stationary points along Distances and bond lengths the reaction coordinate d PB, Å d PH, Å d BH, Å d HH, Å cis TS gauche-pd

6 Figures ΔE, kj mol trans-1 gauche Ф P-C-C-B, degree Figure S1. Relaxed scan of the potential energy surface with respect to the PCCB torsion angle in Mes 2 PCH 2 CH 2 B(C 6 F 5 ) 2, 1, for an estimation of the energy required for isomerization of conformer gauche-1 to conformer trans-1. The values of the potential energy, calculated at the SCS-MP2/ccpVTZ//B97D/6-31G(d) level of theory, are shown with respect to the energy of trans ΔE, kj mol trans-pd1 gauche-pd Ф P-C-C-B, degree Figure S2. Relaxed scan of the potential energy surface with respect to the PCCB torsion angle in the hydrogenated product of 1, Mes 2 PH + CH 2 CH 2 BH (C 6 F 5 ) 2, for an estimation of the energy required for isomerization of conformer gauche-pd1 to conformer trans-pd1. The values of the potential energy, calculated at the SCS-MP2/cc-pVTZ//B97D/6-31G(d) level of theory, are shown with respect to the energy of trans-pd1. 6

7 7

8 Figure S3. Fully-optimized (B97D/6 31G(d)) structure of two closely lying trans monomers of Mes 2 PCHPhCH 2 B(C 6 F 5 ) 2 (2). The calculated intermolecular P B' and P' B distances are of the order of 5.8 Å. Color code: P yellow, B pink, F green, C grey, H white. Figure S4. Fully-optimized (B97D/6 31G(d)) structures of the trans conformers of Mes 2 PCH 2 CH(SiMe 3 )B(C 6 F 5 ) 2, trans-3, in (a), and Mes 2 PCHMeCH 2 B(C 6 F 5 ) 2, trans-4, in (b). The calculated intramolecular PB distance and PCCB torsion angle are equal to 3.93 Å and 111 in (a), and 4.00 Å and 138 in (b). Color code: P yellow, B pink, F green, C grey, H white, Si (in (a)) orange. 8

9 Figure S5. Fully-optimized (B97D/6 31G(d)) structure of dimer-4 composed of trans monomers of Mes 2 PCHMeCH 2 B(C 6 F 5 ) 2 (4). The calculated intermolecular P B' and P' B distances are of the order of 4.5 Å. Color code: P yellow, B pink, F green, C grey, H white. 9

10 Optimized Cartesian coordinates H 2 (optimized at B97D/6-31G* level in gas phase) H H H 2 (optimized at B97D/6-31+G** level in gas phase) H H H 2 (optimized at B97D/6-31+G** level in solvent phase) H H (optimized at B97D/6-31G* level in gas phase) C C C C C C B C C C C C C F F F F F F F F F F P C C C C C C C C C C C C C C C C C C C C

11 H H H H H H H H H H H H H H H H H H H H H H H H H H (optimized at B97D/6-31+G** level in gas phase) C C C C C C B C C C C C C F F F F F F F F F F P C C C C C C C C C

12 C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H (optimized at B97D/6-31+G** level in solvent phase) C C C C C C B C C C C C C F F F F F F F F F

13 F P C C C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H gauche-1 (optimized at B97D/6-31G level in gas phase) C C C C C C B C C C C

14 C C F F F F F F F F F F C C P C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H gauche-1 (optimized at B97D/6-31+G** level in gas phase) 14

15 C C C C C C B C C C C C C F F F F F F F F F F C C P C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H

16 H H H H H H H H H gauche-1 (optimized at B97D/6-31+G** level in solvent phase) C C C C C C B C C C C C C F F F F F F F F F F C C P C C C C C C C C C C C C C C C C C C H H H H H H

17 H H H H H H H H H H H H H H H H H H H H trans-1 (optimized at B97D/6-31G level in gas phase) C C C C C C B C C C C C C F F F F F F F F F F C C P C C C C C C C C C C C C C

18 C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H trans-1 (optimized at B97D/6-31+G** level in solvent phase) C C C C C C B C C C C C C F F F F F F F F F F C C P C C

19 C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H TS1a (optimized at B97D/6-31G level in gas phase) C C C C C C P C C C C C C C C C C

20 C C C C B C C C C C C F F F F F C C C C C C F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H TS1a (optimized at B97D/6-31+G** level in gas phase) C C C C

21 C C P C C C C C C C C C C C C C C B C C C C C C F F F F F C C C C C C F F F F F H H H H H H H H H H H H H H H H H H H H H

22 H H H H H H H TS1a (optimized at B97D/6-31+G** level in solvent phase) C C C C C C P C C C C C C C C C C C C C C B C C C C C C F F F F F C C C C C C F F F F F H H H H H H H H

23 H H H H H H H H H H H H H H H H H H H H gauche-pd1 (optimized at B97D/6-31G level in gas phase) C C C C C C P C C C C C C C C C C C C C C B C C C C C C F F F F F C C C C C C

24 F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H gauche-pd1 (optimized at B97D/6-31+G** level in gas phase) C C C C C C P C C C C C C C C C C C C C C B C C C C

25 C C F F F F F C C C C C C F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H gauche-pd1 (optimized at B97D/6-31+G** level in solvent phase) C C C C C C P C C C C C C

26 C C C C C C C C B C C C C C C F F F F F C C C C C C F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H trans-pd1 (optimized at B97D/6-31G level in gas phase) 26

27 C C C C C C B C C C C C C F F F F F F F F F F C C P C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H H

28 H H H H H H H H H H H trans-pd1 (optimized at B97D/6-31+G** level in gas phase) C C C C C C B C C C C C C F F F F F F F F F F C C P C C C C C C C C C C C C C C C C C C H H H H

29 H H H H H H H H H H H H H H H H H H H H H H H H trans-pd1 (optimized at B97D/6-31+G** level in solvent phase) C C C C C C B C C C C C C F F F F F F F F F F C C P C C C C C C C C C

30 C C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H dimer-1 (optimized at B97D/6-31G level in gas phase) C C C C C C P C C C C C C C C C C C C C C B

31 C C C C C C F F F F F C C C C C C F F F F F C P C C C C C C C C C C B C C C C C C F F F F F C C C C C C F F F F F C C C C

32 C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H TS1b (optimized at B97D/6-31G level in gas phase) C C