Supporting Information Computational Part
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1 Supporting Information Computational Part Ruthenium-Catalyzed Alkyne trans-hydrometalation: Mechanistic Insights and Preparative Implications Dragoş Adrian Roşca, Karin Radkowski, Larry M. Wolf, Minal Wagh, Richard Goddard, Walter Thiel, Alois Fürstner* Max-Planck-Institut für Kohlenforschung, D Mülheim/Ruhr, Germany Table of Contents 1. Computational Methods S2 2. Orbital Interaction Diagram Construction S3 3. Hydrostannation to Form the Minor Constitutional Isomer Z-prod 4. Energy Table for All Structures 5. Coordinates 6. References S7 S8 S9 S41 S1
2 1. Computational Methods All geometry optimizations were performed using the M06 1 functional. The def2-svp 2 basis set was used for all atoms. The 28 inner-shell core electrons of the ruthenium atom were described by the corresponding def2 effective core potential 3 accounting for scalar relativistic effects (def2- ecp). Stationary points were characterized by evaluating the harmonic vibrational frequencies at the optimized geometries. Zero-point vibrational energies (ZPVE) were computed from the corresponding harmonic vibrational frequencies without scaling. Relative free energies ( G) were determined at standard pressure (1 bar) and at room temperature (298 K). The thermal and entropic contributions were evaluated within the rigid-rotor harmonic-oscillator approximation. Solvation contributions were included for dichloromethane on the optimized gas-phase geometries employing the SMD solvation model 4 using the same functional and the def2-tzvp basis set. All calculations were performed using Gaussian09 with the ultrafine grid. 5 Decomposition analysis was performed on the M06/def2-TZVP optimized geometries of [Cp*Ru(Cl)(CH 3 C CCH 3 )] and [Cp*Ru(Cl)(E-2-butene)] using the ADF program package at the M06 level in conjunction with a triple-ζ-quality basis set using uncontracted Slater-type orbitals (STOs) 7 augmented with two sets of polarization functions for all atoms; all electrons were included (i.e., inner core electrons were not described by a frozen core). Scalar relativistic effects were accounted for using the zeroth-order regular approximation (ZORA). 8 S2
3 2. Orbital Interaction Diagram Construction (Figure 4). The orbital interaction diagram from Figure was constructed using perturbation theory (Eq. 1). The relevant fragment orbitals are shown (Figure S1 and S2). The overlap integrals and Fock interaction elements were used in the diagram construction. Figure S1. Fragment orbitals for the [Cp*Ru(Cl)(CH 3 C CCH 3 )] complex. Figure S2. Fragment orbitals for the [Cp*Ru(Cl)(E-2-butene)] complex. S3
4 Eq 1. Perturbation theory derived expression for determining the interaction between two orbitals. where S ij is the overlap integral between orbitals i and j, F ij is the Fock matrix element between orbitals i and j, and ε i is the orbital energy for i. Table S1. Fragment orbital energies for the [Cp*Ru(Cl)(CH 3 C CCH 3 )] complex. ε (ev) Ru_LUMO_a Ru_LUMO+1_a Ru_HOMO_a Ru_HOMO-1_a yne_lumo_a yne_lumo+1_a yne_homo_a yne_homo-1_a Table S2. Overlap integrals between the fragment orbitals for the [Cp*Ru(Cl)(CH 3 C CCH 3 )] complex. Overlap Matrix (S ij ) yne_lumo_a yne_lumo+1_a yne_homo_a yne_homo-1_a Ru_LUMO_a Ru_LUMO+1_a Ru_HOMO_a Ru_HOMO-1_a S4
5 Table S3. The corresponding Fock interaction matrix elements for the [Cp*Ru(Cl)(CH 3 C CCH 3 )] complex. Fock Matrix (F ij (ev)) yne_lumo_a yne_lumo+1_a yne_homo_a yne_homo-1_a Ru_LUMO_a Ru_LUMO+1_a Ru_HOMO_a Ru_HOMO-1_a Table S4. Orbital interaction matrix elements computed using eq. 1 for the [Cp*Ru(Cl)(CH 3 C CCH 3 )] complex. Interaction Energy ( ε ij ) yne_lumo_a yne_lumo+1_a yne_homo_a yne_homo-1_a Ru_LUMO_a Ru_LUMO+1_a Ru_HOMO_a Ru_HOMO-1_a Table S5. Fragment orbital energies for the [Cp*Ru(Cl)(E-2-butene)] complex. ε (ev) Ru_LUMO Ru_HOMO ene_lumo ene_homo Table S6. Overlap integrals between the fragment orbitals for the [Cp*Ru(Cl)(E-2-butene)] complex. Overlap Matrix (S ij ) ene_lumo ene_homo Ru_LUMO 0.21 Ru_HOMO 0.17 S5
6 Table S7. The corresponding Fock interaction matrix elements for the [Cp*Ru(Cl)(E-2-butene)] complex. Fock Matrix (F ij (ev)) ene_lumo ene_homo Ru_LUMO Ru_HOMO Table S8. Orbital interaction matric elements computed using eq. 1 for the [Cp*Ru(Cl)(E-2- butene)] complex. Interaction Energy ( ε ij ) ene_lumo ene_homo Ru_LUMO Ru_HOMO S6
7 3. Hydrostannation to Form the Minor Constitutional Isomer Z-prod The regioisomeric pathway leading to the constitutional isomer from addition of H and Sn on opposite carbon atoms was also investigated (Figure S3). The H---Cl hydrogen bond present in the complex of INT1 is not feasible in this pathway (INT1 ). In solution the hydrogen bond accounts for an additional 1.1 kcal/mol, while in the gas phase the interaction is ~2.8 kcal/mol. It is this interaction that accounts for the preference for the pathway from INT1. Figure S3. Gibbs free energy profile (in units of kcal mol -1 ) for the formation of the minor constitutional isomer Z-prod S7
8 4. Energy table for Hydrostannation. Table S9. Listed are the SCF energy, zero point vibrational energy (ZPVE), enthalpy correction (H corr ), and Gibbs free energy correction (G corr ) determined on the gas-phase geometries for all stationary points calculated. The single imaginary frequency (υ i cm -1 ) is also listed for all transition states. Single point solvent (DCM) corrected SCF energies on the gas phase geometries are also tabulated. All energies are in atomic units. SCF gas SCF DCM ZPVE H corr G corr υ i (cm -1 ) INT INT TS i50 INT TS i357 INT TS2-Z i60 Z-prod TS i19 INT TS i135 INT TS5-E i40 E-prod TS i139 TS i23 INT TS i36 INT-1` TS1-2` i358 INT-2` TS2-Z` i84 Z-prod` TS2-3` i42 INT-3` TS3-4` i36 INT-4` INT0-Si INT0 -Si HSnMe S8
9 5. Coordinates Cartesian coordinates (Å) INT0 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H O H H H H S9
10 INT0 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H O H H H H H S10
11 TS0-0 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H O H H H H S11
12 INT1 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H O H H Sn C H H H C H H H C H H H S12
13 TS1-2 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H Sn H C H H H C H H H C H H H H H O H S13
14 INT2 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H Sn C H H H C H H H C H H H H H O H S14
15 TS2-Z Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H O H Sn C H H H C H H H C H H H S15
16 Z-prod Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H Sn C H H H C H H H C H H H O H S16
17 TS2-3 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H Sn C H H H C H H H C H H H O H S17
18 INT-3 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H Sn O H C H H H C H H H C H H H H S18
19 TS3-5 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H O H Sn C H H H C H H H C H H H S19
20 INT-5 Ru Cl C C C H C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H O H Sn C H H H C H H H C H H H S20
21 TS5-E Ru Cl C C C H C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H O H Sn C H H H C H H H C H H H S21
22 E-prod Ru Cl C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H Sn O H C H H H C H H H C H H H C H H H H S22
23 TS2-5 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H O H Sn C H H H C H H H C H H H S23
24 TS3-4 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H Sn C H H H C H H H C H H H O H H S24
25 INT-4 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H Sn C H H H C H H H C H H H O H S25
26 TS4-5 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H Sn C H H H C H H H C H H H O H S26
27 INT1 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H Sn C H H H C H H H C H H H H H O H H S27
28 TS1-2 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H Sn H C H H H C H H H C H H H H H H O H S28
29 INT2 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H Sn C H H H C H H H C H H H H H O H H S29
30 TS2-Z Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H Sn C H H H C H H H C H H H H O H S30
31 Z-prod Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H Sn C H H H C H H H C H H H H O H S31
32 TS2-3 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H Sn C H H H C H H H C H H H H O H H S32
33 INT3 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H Sn C H H H C H H H C H H H H H O H H S33
34 TS3-4 Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H Sn C H H H C H H H C H H H H H O H S34
35 INT4 Ru Cl C C H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H Sn C H H H C H H H C H H H H H O H S35
36 INT0-Si Ru Cl C C Si C C C C C C C H H H C H H H C H H H C H H H C H H H H O C C C H H H H H H H H H H H S36
37 INT0 -Si Ru Cl C C C Si C C C C C C H H H C H H H C H H H C H H H C H H H C C H O H H H H H H H H C H H H S37
38 [Cp*Ru(Cl)(E-2-butene)] Ru Cl C C H H C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H H S38
39 [Cp*Ru(Cl)(CH 3 C CCH 3 )] Ru Cl C C C C C C C C C C H H H C H H H C H H H C H H H C H H H H H H H H H S39
40 Cp*RuCl Ru Cl C C C C C C H H H C H H H C H H H C H H H C H H H CH 3 C CCH 3 C C C C H H H H H H E-2-butene C C H H C C H H H H H H S40
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