Supporting information. Formation of A New Strong Basic Nitrogen Anion by Metal Oxide Modification

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1 Supporting information Formation of A ew Strong Basic itrogen Anion by Metal Oxide Modification Masazumi Tamura,*,, Ryota Kishi, Akira akayama,*,, Yoshinao akagawa, Jun-ya Hasegawa, Keiichi Tomishige*, Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai , Japan JST, PRESTO, Honcho Kawaguchi, Saitama , Japan Institute for Catalysis, Hokkaido University, Kita 21 ishi 10, Kita-ku, Sapporo , Japan mtamura@erec.che.tohoku.ac.jp, nakayama@cat.hokudai.ac.jp, tomi@erec.che.tohoku.ac.jp Table of contents 1. Typical procedure for Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate (Page S3) 2. FTIR analysis of methanol and 2-cyanopyridine adsorption (Page S3) 3. UV-vis analysis (Page S3) 4. Supporting Tables Table S1. The relationship between the pk a and Log(TOF) of the organic base compounds in the hydromethoxylation of acrylonitrile, and estimation of pk a of CeO 2 +2-cyanopyridine, CeO 2, and 2-cyanopyridine (Detailed data of Figure 1) (Page S4) Table S2. The relationship between the pk a and Log(TOF) of the organic base compounds in the Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate, and estimation of pk a of CeO 2 +2-cyanopyridine, CeO 2, and 2-cyanopyridine (Detailed data of Figure S1) (Page S5) Table S3. Effect of calcination temperature of CeO 2 on the initial reaction rate for hydoromethoxylation of acrylonitrile (Page S6) Table S4. Relationship between activity and Hammett parameter of p-(5-) or m-(4-)substituted 2-cyanopyridines in the hydromethoxylation of acrylonitrile using CeO 2 and 2-cyanopyridine derivatives (Page S7) Table S5. The effect of methanol concentration in the hydromethoxylation of acrylonitrile using CeO cyanopyridine (Page S8) Table S6. The effect of methanol concentration in the hydromethoxylation of acrylonitrile using CeO 2 (Page S8) Table S7. The effect of acrylonitrile concentration in the hydromethoxylation of acrylonitrile using CeO cyanopyridine (Page S9) Table S8. The effect of acrylonitrile concentration in the hydromethoxylation of acrylonitrile using CeO 2 (Page S9) Table S9. Isotope effect of methanol in hydromethoxylation of acrylonitrile with CH 3 OH and CH 3 OD using CeO 2 and 2-cyanopyridine (Page S10) Table S10. Relationship between reactivity and Hammett parameter in the hydromethoxylation of various conjugated olefins using CeO 2 and 2-cyanopyridine (Page S11) Table S11. Effect of reaction temperatures in hydromethoxylation of acrylonitrile using CeO 2 and S1

2 CeO 2 +2-cyanopyridine (Page S12) Table S12. Adsorption energy of the representative nitriles in the adsorption structure similar to St-C (Page S13) 5. Supporting Figures Figure S1. The relationship between the pka and Log(TOF) of the organic base compounds in the Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate, and estimation of pka of CeO 2 +2-cyanopyridine, CeO 2, and 2-cyanopyridine (Page S14) Figure S2. Effect of calcination temperatures of CeO 2 in hydromethoxylation of acrylonitrile using CeO 2 +2-cyanopyridine (Page S15) Figure S3. Photographs of metal oxide solutions, and metal oxide+2-cyanopyridine solutions (Page S16) Figure S4. Transmission FTIR spectra of methanol adspecies on (a) CeO 2 and (b) CeO 2 +2-cyanopyridine in the region of cm -1 (Page S17) Figure S5. (a-c) PDOS summed over all atoms (black), Ce atoms (dark brown), O atoms (red), and all atoms of 2-cyanopyrdine (blue) at (a) St-A, (b) St-B, and (c) St-C on CeO 2 (111). (d-f) PDOS of C atoms (black), atoms (blue), and H atoms (dark red) of 2-cyanopyridine at (d) St-A, (e) St-B, and (f) St-C on CeO 2 (111). The PDOS is shifted so that the upper edge of the valence band of the CeO 2 (111) slab becomes zero (Page S18) Figure S6. Adsorption structures of methanol on the CeO 2 (111) surface (Page S19) Figure S7. Adsorption structures of representative nitrile additives given in Table S12 (Page S20) Figure S8. Snapshot of the MD simulation during the nucleophilic attack of methoxy species using DBU catalyst (Page S21) Figure S9. Mean force acting on the distance between O atom of the attacking methanol moiety and C atom of acrylonitrile (Page S22) 6. Reference (Page S23) S2

3 1. Typical procedure for Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate. CeO mg (1 mmol), 2-cyanopyridine (1 mmol), ethanol 3.0 g (65 mmol), benzaldehyde (3 mmol) and ethyl cyanoacetate (4 mmol) were added to a reaction vessel, and the mixture was vigorously stirred at 500 rpm at 303 K under air. After the reaction, the reaction mixture was filtrated, diluted with acetone, and transferred to a vial. The products were analyzed using GC equipped with a FID detector and CP-Sil5 capillary column (length 50 m, i.d mm, film thickness 0.25 µm). Conversion and yield of products were determined based on benzaldehyde by GC using 1,4-dioxane as an internal standard. Products were also identified using standard compounds and GC-MS equipped with the same detector and capillary column. 2. FTIR analysis of methanol and 2-cyanopyridine adsorption FTIR spectra were recorded by transmission method with a ICOLET 6700 spectrometer (Thermo Scientific) equipped with a liquid nitrogen-cooled MCT (HgCdTe) detector (resolution 4 cm -1 ), using an in-situ IR cell with CaF 2 windows, which was connected to a conventional gas flow system. CeO 2 (~80 mg) was pressed into a self-supporting wafer (20 mm diameter) and mounted into the IR cell. Adsorption of methanol and 2-cyanopyridine was carried out in the following method: The catalyst was preheated at 873 K under He (50 ml min -1 )/O 2 (10 ml min -1 ) flow for 10 min. Then the catalyst was cooled down to 323 K under a He flow. Methanol (2 µl) was injected into the gas line heated at 523 K under a He flow, which was fed to the in-situ IR cell. For adsorption of both methanol and 2-cyanopyridine, 2-cyanopyrdine (1 µl) was injected into the gas line heated at 523 K under a He flow, which was fed to the in-situ IR cell. After that, methanol was injected into the same gas line under a He flow. The spectrum change was monitored and after it was stable spectra were obtained by subtraction of the reference spectrum of CeO 2 measured at 323 K under He flow. 3. UV-vis analysis UV-vis diffuse reflectance spectra were measured with Shimadzu UV 2450 spectrophotometer with the integration sphere diffuse reflectance attachment (ISR-2200 Shimadzu) and a photomultiplier detector. Pure BaSO 4 was used as a reference sample. The solution samples were added in a transparent quartz cell and the cell was located at the integration sphere diffuse reflectance attachment. The spectra were measured in the region of 350 ~ 800 nm at room temperature. The scan speed is middle and the resolution of spectra is 0.1 nm. The sample without CeO 2 sample was measured by the conventional transmission method on the same spectrophotometer using the 1-cm path length transparent quartz cell. S3

4 4. Supporting Tables Table S1. The relationship between the pk a and Log(TOF) of the organic base compounds in the hydromethoxylation of acrylonitrile, and estimation of pk a of CeO 2 +2-cyanopyridine, CeO 2, and 2-cyanopyridine (Detailed data of Figure 1). Catalyst [Amount / mmol] Amount / mmol t Conversion Yield DBU a TOF c / h / % / % / mmol h -1 mmolcat DMAP a Methoxy-pyridine a Pyridine a CeO2+2-cyanopyridine b d CeO2 b Cyanopyridine b areaction conditions: acrylonitrile (40 mmol), methanol (60 mmol), organic base compound ( mmol), 323 K, 0-24 h. bthese data were quoted from the previous work [1]. Reaction conditions: acrylonitrile (10 mmol), methanol (15 mmol), CeO 2(1 mmol) and/or 2-cyanopyridine (1 mmol), 323 K, 0-48 h. ctof was calculated by the following equation: TOF (h -1 ) = (Produced amount of 3-methoxypropionitrile (mmol)) / (Reaction time (h)) / catalyst amount (mmol)) dthe TOF was calculated on the basis of adsorption amount of 2-cyanopyridine (0.28 mmol/g) [1]. S4

5 Table S2. The relationship between the pk a and Log(TOF) of the organic base compounds in the Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate, and estimation of pk a of CeO 2 +2-cyanopyridine, CeO 2, and 2-cyanopyridine (Detailed data of Figure S1). O CO 2 Et Catalyst H + C CO 2 Et + H 2 O Ethanol (3 g) C 303 K (3 mmol) (4 mmol) Catalyst [Amount / mmol] Amount / mmol t Conversion Yield TOF a / min / % / % / mmol min -1 mmolcat -1 DMAP Methoxy-pyridine Pyridine CeO2+2-cyanopyridine b CeO c Cyanopyridine Reaction conditions: benzaldehyde (3 mmol), ethyl cyanoacetate (4 mmol), organic base compound (0.1-5 mmol), ethanol (3 g), 303 K, 0-60 min. a TOF was calculated by the following equation: TOF (h -1 ) = (Produced amount of 3-methoxypropionitrile (mmol)) / (Reaction time (h)) / catalyst amount (mmol)) b The TOF was calculated on the basis of adsorption amount of 2-cyanopyridine (0.28 mmol/g) [1]. c The TOF was calculated on the basis of surface Ce amount (0.95 mmol/g). S5

6 Table S3. Effect of calcination temperature of CeO 2 on the initial reaction rate for hydoromethoxylation of acrylonitrile. Tcalcination SBET a t Conversion Selectivity V b V c / K / m 2 g -1 / h / % / % / mmol h -1 gceo2-1 / mmol h -1 m > > > > Reaction conditions: acrylonitrile (10 mmol), methanol (15 mmol), CeO 2 (1 mmol), 2-cyanopyridine (1 mmol), 323 K, air, 0.5 h. a surface area was measured by BET method. bv (mmol h -1 g -1 ) = (Amount of 3-methoxypropionitrile (mmol))/(reaction time (h))/(amount of CeO 2 (g)). cv (mmol h -1 m -2 )= V (mmol h -1 g -1 ) / (surface area of CeO 2 (m 2 g -1 )) S6

7 Table S4. Relationship between activity and Hammett parameter of p-(5-) or m-(4-)substituted 2-cyanopyridines in the hydromethoxylation of acrylonitrile using CeO 2 and 2-cyanopyridine derivatives (Detailed data of Figure 2). C CeO 2 + CH 3 OH + C R 323 K, air O C Entry -R σ a t Conversion. Selectivity Yield V Amount of amide / h / % / % / % / mmol h -1 gceo2-1 / mmol 1 b p-och > > b p-ch > > c p-h > > d p-f > > d p-cl > > m-o > > a Hammett parameters quoted from the paper (H.C. Brown, J. Org. Chem. 23 (1958) 420.) Reaction conditions: acrylonitrile (10 mmol), methanol (15 mmol), CeO 2 (1 mmol), 2-cyanopyridine derivative (1 mmol), 323 K, air, h. Pretreatment time: b 3 h, c 1 h, d 0.5 h. S7

8 Table S5. The effect of methanol concentration in the hydromethoxylation of acrylonitrile using CeO cyanopyridine (Detailed data of Figure 4(a) using CeO 2 +2-cyanopyridine). Concentration Amount of products / mmol Amount of methanol t Conv. Sel. Yield V of methanol 2-Cyanopyridine Imidate a Amide / mmol / M / h /% /% /% / mmol h -1 gcat Reaction conditions: acrylonitrile (40 mmol), methanol (8-14 mmol), CeO 2 (1 mmol), 2-cyanopyridine (0 or 1 mmol), 323 K, air. a Methyl pyridine-2-carboximidate. Table S6. The effect of methanol concentration in the hydromethoxylation of acrylonitrile using CeO 2 (Detailed data of Figure 4(a) using CeO 2 ). Amount of methanol Concentration of methanol t Conversion Selectivity Yield V / mmol / M / h /% /% /% / mmol h -1 gcat Reaction conditions: acrylonitrile (40 mmol), methanol (8-14 mmol), CeO 2 (1 mmol), 323 K, air. S8

9 Table S7. The effect of acrylonitrile concentration in the hydromethoxylation of acrylonitrile using CeO cyanopyridine (Detailed data of Figure 4(b) using CeO 2 +2-cyanopyridine). Amount of acrylonitrile Concentration of t Conv. Sel. Yield V Amount of products / mmol / mmol acrylonitrile / M / h / % / % / % / mmol h -1 g -1 2-Cyanopyridine Imidate a Amide Reaction conditions: acrylonitrile (5-30 mmol), methanol (100 mmol), CeO 2 (1 mmol), 2-cyanopyridine (1 mmol), 323 K, air, 0.5 h. a Methyl pyridine-2-carboximidate. Table S8. The effect of acrylonitrile concentration in the hydromethoxylation of acrylonitrile using CeO 2 (Detailed data of Figure 4(b) using CeO 2 ). Amount of acrylonitrile Concentration of acrylonitrile t Conversion Selectivity Yield V / mmol / M / h / % / % / % / mmol h -1 g Reaction conditions: acrylonitrile (5-30 mmol), methanol (100 mmol), CeO 2 (1 mmol), 323 K, air, 0.5 h. S9

10 Table S9. Isotope effect of methanol in hydromethoxylation of acrylonitrile with CH 3 OH and CH 3 OD using CeO 2 and 2-cyanopyridine (Detailed data of Figure 5). Amount of products / mmol Alcohol source t / h Conversion. /% Selectivity /% Yield /% 2-Cyanopyridine Imidate a Amide CH3OH CH3OD Reaction conditions: acrylonitrile (10 mmol), CH 3OH or CH 3OD (15 mmol), CeO 2 (1 mmol), 2-cyanopyridine (1 mmol), 323 K, air, 0.5 h. amethyl pyridine-2-carboximidate S10

11 Table S10. Relationship between reactivity and Hammett parameter in the hydromethoxylation of various conjugated olefins using CeO 2 and 2-cyanopyridine (Detailed data of Figure 6). CH 3 OH + R CeO Cyanopyridine 323 K, air O R -R t / h Conversion / % Selectivity / % Yield / % Reaction rate / mmo h -1 g -1 Amount / mmol 2-Cyanopyridine Imidate a Amide -C > COCH > > > > > > > COOCH > > > > > COH Reaction conditions: conjugated olefin (10 mmol), methanol (15 mmol), CeO 2 (1 mmol), 2-cyanopyridine (4 mmol), 323 K, air, h. a Methyl pyridine-2-carboximidate. S11

12 Table S11. Effect of reaction temperatures in hydromethoxylation of acrylonitrile using CeO 2 and CeO 2 +2-cyanopyridine (Detailed data of Figure 7). Catalyst T/ K t / h Conversion /% Yield /% Reaction rate (V)/ mol h -1 g CeO2 + 2-Cyanopyridine CeO Reaction conditions: acrylonitrile (10 mmol), methanol (15 mmol), CeO 2 (1 mmol)+2-cyanopyridine (1 mmol) or CeO 2 (3 mmol), K, air. S12

13 Table S12. Adsorption energy of the representative nitriles in the adsorption structure similar to St-C. Entry itrile V a (mmol h 1 g 1 ) EA (ev) 1 C C C 4 C < C 5 C C a The reaction rate was quoted from Table 3. S13

14 5. Supporting Figures O H + C CO 2 Et (3 mmol) (4 mmol) Catalyst Ethanol (3 g) 303 K CO 2 Et + H 2 O C 1 CeO 2 + C (R 2 =0.99) Log(TOF / min -1 ) O CeO 2 C pk a (in CH 3 C) Figure S1. The relationship between the pk a and Log(TOF) of the organic base compounds in the Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate, and estimation of pk a of CeO 2 +2-cyanopyridine, CeO 2, and 2-cyanopyridine. The detailed data are shown in Table S2. S14

15 (a) (b) 0.6 V / mmol h -1 g CeO V' / mmol h -1 m Calcination temperature / K Figure S2. Effect of calcination temperatures of CeO 2 in hydromethoxylation of acrylonitrile using CeO 2 +2-cyanopyridine. (a) Reaction rate per CeO 2 amount (mmol h -1 g CeO2-1 ) vs calcination temperature, (b) Reaction rate per surface area of CeO 2 (mmol h -1 m -2 ) vs calcination temperature. Reaction conditions: acrylonitrile (10 mmol), methanol (15 mmol), CeO 2 (1 mmol), 2-cyanopyridine (1 mmol), 323 K, air, 0.5 h Calcination temperature / K S15

16 Figure S3. Photographs of metal oxide solutions, and metal oxide+2-cyanopyridine solutions. (a)al 2 O 3, (b) Al 2 O 3 +2-cyanopyridine, (c) ZrO 2, (d) ZrO 2 +2-cyanopyridine, (e) MgO, (f) MgO+2-cyanopyridine, (g) TiO 2, (h) TiO 2 +2-cyanopyridine, (i) Y 2 O 3, (j) Y 2 O 3 +2-cyanopyridine, (k) SiO 2, (l) SiO 2 +2-cyanopyridine. Conditions: methanol (20 mmol), metal oxide (1 mmol), 2-cyanopyridine (2 mmol), 303 K. S16

17 Absorbance (b) Wavenumber / cm -1 (a) 950 Figure S4. Transmission FTIR spectra of methanol adspecies on (a) CeO 2 and (b) CeO 2 +2-cyanopyridine in the region of cm -1. S17

18 (a) total Ce O 2-cyanopyridine (d) C H St-A St-A (b) total Ce O 2-cyanopyridine (e) C H St-B St-B (c) total Ce O 2-cyanopyridine (f) C H St-C St-C Energy / ev Energy / ev Figure S5. (a-c) PDOS summed over all atoms (black), Ce atoms (dark brown), O atoms (red), and all atoms of 2-cyanopyrdine (blue) at (a) St-A, (b) St-B, and (c) St-C on CeO 2 (111). (d-f) PDOS of C atoms (black), atoms (blue), and H atoms (dark red) of 2-cyanopyridine at (d) St-A, (e) St-B, and (f) St-C on CeO 2 (111). The PDOS is shifted so that the upper edge of the valence band of the CeO 2 (111) slab becomes zero. S18

19 Figure S6. Adsorption structures of methanol on the CeO 2 (111) surface. (a) Molecular state adsorption, (b) dissociative state adsorption, (c) dissociative state adsorption where a proton is diffused further from the methoxy moiety. The atoms are color coded as follows: gray, H; dark gray, C; red O; dark yellow, Ce. S19

20 Figure S7. Adsorption structures of representative nitrile additives given in Table S12. (a) 3-cyanopyridine, (b) 4-cyanopyridine, (c) (2-pyridyl)acetonitrile, (d) 2-cyanopyrazine, (e) 1-isoquinolinecarbonitrile, and (f) 2-quinolinecarbonitrile. The atoms are color coded as follows: gray, H; dark gray, C; blue, ; red O; dark yellow, Ce. S20

21 Figure S8. Snapshot of the MD simulation during the nucleophilic attack of methoxy species using DBU catalyst. Blue shaded circle represents the base site and yellow shaded shows the attacking methoxy species. The O-C distance is fixed at 2.0 Å in Figure 11. The atoms are color coded as follows: gray, H; dark gray, C; blue, ; red O. S21

22 Force / hartreebohr CeO₂+2-Py cyanopyridine CeO₂ 2 DBU Distance O-C / Å Figure S9. Mean force acting on the distance between O atom of the attacking methanol moiety and C atom of acrylonitrile. S22

23 6. References [1] Tamura, M.; Kishi, R.; akagawa, Y.; Tomishige, K. at. Commun. 2015, 6, S23