Supporting Information Mechanism of Ullmann Coupling Reaction of Chloroarene on Au/Pd Alloy Nanocluster: A DFT Study

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1 Supporting Information Mechanism of Ullmann Coupling Reaction of Chloroarene on Au/Pd Alloy Nanocluster: A DFT Study Jittima Meeprasert 1, Supawadee Namuangruk 1,*, Bundet Boekfa 2,3, Raghu N. Dhital 4, Hidehiro Sakurai 4, Masahiro Ehara 2,3,* 1 National Nanotechnology Center (NANOTEC), Thailand Science Park, Patumthani 12120, Thailand 2 Institute for Molecular Science, Nishigo-naka 38, Myodai-ji, Okazaki , Japan 3 Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Kyoto , Japan 4 Division of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka , Japan Charge analysis and density difference plot for EP n adsorption on neutral Au 10 Pd 10 N-ethylpyrrolidone (EP) is a monomer of poly(n-vinylpyrrolidone) (PVP) which was used as a support polymer of AuPd NC in the experiment We examined the effect of PVP surrounding the AuPd NC by calculating charge transfer between adsorbed EP n (n=1 4) and neutral Au 10 Pd 10 NC. Figure S1 shows the electron density difference between before and after EP n adsorption. Table S1 shows that the negative charges on Au 10 Pd 10 NC are increased with the increase of EP molecules. EP 1 -Au 10 Pd 10 EP 2 -Au 10 Pd 10 EP 3 -Au 10 Pd 10 EP 4 -Au 10 Pd 10 Figure S1. Electron density difference plot for EP n adsorption on neutral Au 10 Pd 10 NC representing in front view (up) and side view (down). Cyan and purple regions represent the decrease and increase of electron density, respectively. S1

2 Table S1. Adsorption energies and gross charges on EP n (n=1 4) and neutral Au 10 Pd 10 after EP adsorption. Complex Adsorption energy a Δq(EP n ) Δq(Au 10 Pd 10 ) (kcal/mol) b EP 1 -Au 10 Pd (-26.69) EP 2 -Au 10 Pd (-24.52) EP 3 -Au 10 Pd (-24.41) EP 4 -Au 10 Pd (-24.30) a Adsorption energy per EP molecule is in parentheses. b Adsorption energy of EP 1 on Au 10 Pd 10 is -19 kcal/mol. Table S2. The relative energy and activation energy (kcal/mol) of the Pathway I calculated by M06L/6-31G(d,p) level of theory. E ele, E 0, and G are the electronic energy, total energy including zero-point energy, and Gibbs free energy at K, respectively. relative energy [activation energy] E ele E 0 G ArCl_X TS-A [7.2] [6.7] -8.3 [7.2] Ar-X-Cl DMFOH_ArX_w TS-B_w [24.0] [18.8] -9.6 [19.1] Me 2 NH-CO 2 _ArXH_w DMFOH_ArX TS-B -5.4 [31.9] [28.6] 4.3 [28.5] Me 2 NH-CO 2 _ArXH Me 2 NH_ArXH Ar-X-H ArCl_HXAr TS-Cc [12.1] [10.5] [12.2] TS-Cs [12.2] [11.2] [14.5] Ar_ArXH_Cl TS-Cs [16.2] [14.8] [14.8] HCl_ArXAr Ar-X-Ar TS-D [15.5] [15.6] [16.4] ArAr_X ArAr desorption energy S2

3 Table S3. The relative energy and activation energy (kcal/mol) of the Pathway II calculated by M06L/6-31G(d,p) level of theory. E ele, E 0, and G are the electronic energy, total energy including zero-point energy, and Gibbs free energy at K, respectively. relative energy [activation energy] E ele E 0 G ArCl_X TS-A [7.2] [6.7] -8.3 [7.2] Ar-X-Cl ArCl_ArXCl TS-E [24.6] [23.2] [22.8] Ar-ArXCl-Ar TS-G [7.3] [7.4] [7.3] ArAr_ClXCl ClXCl DMFOH_XCl_w TS-H2-w [21.6] [17.3] [18.1] Me 2 NH-CO 2 _HXCl_w DMFOH_XCl TS-H [30.0] [26.9] [27.2] Me 2 NH-CO 2 _HXCl Me 2 NH_HXCl HXCl TS-H [21.9] [20.0] [18.6] HCl_X HCl desorption energy Analysis of density of states of the three catalytic models, Au 20, Au 10 Pd 10, and Pd 20. A Multifunctinal Wave function Analyzer was used. ( T. Lu, F. Chen, J. Comput. Chem. 33, (2012). Au 20 - Au 10 Pd 10 - Pd 20 - S3

4 a) Au 20 b) Au 10 Pd 10 c) Pd 20 Figure S2. Density of state (DOS) for the three NCs; (a) Au 20, (b) Au 10 Pd 10, and (c) Pd 20. S4

5 Figure S3. Frontier MOs of (a) Au 10 Pd 10 and (b) ArCl-Au 10 Pd 10 (isovalue = 0.02 au) Spin density analysis Figure S4. Spin density difference plot for (a) Au 10 Pd 10 and (b) ArCl-Au 10 Pd 10 (isovalue = au). S5

6 Fukui function analysis Nucleophilic attack: f A qn qn 1 A A Electrophilic attack: f A qn 1 qn A A Note: Electron densities on neutral and anion Au 10 Pd 10 NCs are increased and decreased, respectively, after the ArCl adsorption. Thus, neutral Au 10 Pd 10 NC prefers nucleophilic attack while anion Au 10 Pd 10 NC prefers the electrophilic attack. Labeling atoms for Au 10 Pd 10 Table S4. NBO charge and condensed Fukui function for Au 10 Pd 10 NBO charge Fukui function N N-1 f - Au Pd Au Pd Pd Pd Au Au Au Pd Au Pd Au Au Au Pd Au Pd For f -, the highest value occurs at Pd14 atom, indicating that this atom is preferable site for electrophilic attack. We therefore selected this atom for ArCl adsorption. S6

7 Table S5. NBO charge and condensed Fukui function for Au 10 Pd 10 NBO charge Fukui function N+1 N f + Au Pd Au Pd Pd Pd Au Au Au Pd Au Pd Au Au Au Pd Au Pd For f +, the highest value occurs at Au15 atom, indicating that this atom is preferable site for nucleophilic attack. In case of neutral Au 10 Pd 10 NC, Au would be more preferable for ArCl adsorption than Pd. S7

8 Figure S5. Energy profile for the decomposition of Me 2 NCOOH into Me 2 NH and CO 2 with (blue line) and without (red line) Au 10 Pd 10 NC. Relevant interatomic distances at reaction site are shown in Å. S8

9 Figure S6. Possible structures of (a, b) ArCl_HXAr and (c, d) ArCl_ArXCl. Adsorption energy for each structure is given. S9

10 Figure S7. Structures of intermediates and transition states which appear in Step A, E and G in the pathway II. Relevant interatomic distances at reaction site are shown in Å. S10

11 Figure S8. Structures of intermediates and transition states which appear in Step H2 and H3 in the pathway II. Relevant interatomic distances at reaction site are shown in Å. S11

12 Figure S9. Structures of intermediates and transition states which appear in the H migration and benzene formation in the side reaction pathway. Relevant interatomic distances at reaction site are shown in Å. Table S6. Imaginary vibrational frequency (cm -1 ) and activation energy barrier (kcal/mol) of all transition state structures in the reaction mechanism Structures Imaginary vibrational frequency Activation energy (cm -1 ) (kcal/mol) Homocoupling reaction TS-A TS-B TS-B_w TS-Cc TS-Cs TS-Cs TS-D TS-E TS-G TS-H TS-H2_w TS-H Side reaction TS-H TS-Ar-H S12