Electronic Supporting Information. Ru-Based complexes with quaternary ammonium tags immobilized on mesoporous silica as olefin metathesis catalysts

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1 Electronic Supporting Information RuBased complexes with quaternary ammonium tags immobilized on mesoporous silica as olefin metathesis catalysts Jakub Pastva a, Krzysztof Skowerski b*, Stefan J. Czarnocki b, Naděžda Žilková a, Jiří Čejka a, Zdeněk Bastl a Hynek Balcar a* a J. Heyrovský Institute of Physical Chemistry of the ASCR, v. v. i. Dolejškova 2155/3, Prague 8, Czech Republic b Apeiron Synthesis SA., Duńska 9, Wroclaw, Poland Corresponding authors * balcar@jhinst.cas.cz and krzysztof.skowerski@apeironsynthesis.com Table S1. Amounts of modified sieves and HGIIN + Cl used for the preparation of the catalysts. Weight of Used Catalyst Weight of sieves HGIIN + Cl Catalyst Ru content f supports (mg) applied (wt%) (mg) HGIIN + Cl //SBA15 SBA HGIIN + Cl //MCM41 MCM Silicagel HGIIN + Cl //silica 4 f = fraction of Ru captured on the support Table S2. Amounts of SBA15 and Ru complexes used for the preparation of the catalysts. Weight of Used Weight of Catalyst HGIIN sieves + Catalyst Ru X content supports applied (mg) (wt%) (mg) f HGIIN + I //SBA15 SBA HGIIN + BF 4 //SBA15 SBA HGIIN + PF 6 //SBA15 SBA

2 Intensity Theta, Figure S1. XRD patterns of SBA15 (full line), MCM41 (dashed line) a) 9 8 a cm 3 /g at STP p/p

3 8 7 b) 6 a cm 3 /g at STP p/p Figure S2. a) Adsorption isotherms for SBA15 ( ), MCM41 ( ) and Silicagel 4 ( ). For clarity 2 and 3 cm 3 /g (STP) was added to the adsorption isotherms of Silicagel 4 and MCM41 respectively. Open symbols are used for adsorption branches of the isotherms, filled symbols for desorption branches of the isotherms. b) Adsorption isoterms of SBA15 ( ) and prepared catalyst HGIIN + Cl /SBA15 ( ).Open symbols are used for adsorption branches of the isotherms, filled symbols for desorption branches of the isotherms. a O 1s HGIIN + Cl /SBA15 O (KLL) b O 1s HGIIN + BF 4 /SBA15 O (KLL) Ru 4s INTENSITY (arb.units) O 2s Ru 3s Cl 2p Cl 2s Si 2p Si 2s GHIIN + Cl Ru 3p Ru 3d C 1s INTENSITY (arb.units) O 2s Si 2p Si 2s N 1s F 1s B 1s Cl 2p F (A) F 1s Ru 4s Ru 3s HGN + BF 4 Cl 2s N 1s Ru 3p Ru 3d C 1s BINDING ENERGY (ev) BINDING ENERGY (ev)

4 c O 1s HGIIN + PF 6 /SBA15 O (KLL) d O 1s HGIIN + I /SBA Figure S3 XPS survey scans of HGIIN + X and HGIIN + X /SBA15. X = Cl (a), BF 4 (b), PF 6 (c), I (d). N 1s HGIIN + Cl /SBA15 INTENSITY (arb.units) P 2s F 1s F (KLL) Ru 4s INTENSITY (arb.units) Ru 3s P 2p Cl 2s O (KLL) O 2s HGIIN + PF 6 Cl 2p Si 2p Ru 3p Si 2s Ru 3d C 1s INTENSITY (arb.units) O 2s Si 2p Si 2s I 4p I 4s Cl 2p Cl 2s N 1s Ru 3d I 3d I 3p 3/2 I 3p 1/2 Ru 4s Ru 3s C 1s I 4d GHIIN + I N 1s Ru 3p BINDING ENERGY (ev) BINDING ENERGY (ev) HGIIN + Cl BINDING ENERGY (ev) Figure S4 Typical XP spectrum of N 1s photoelectrons of HGN + Cl and HGN + Cl/SBA15.

5 Figure S5. RCM of 1 with catalysts HGIIN + Cl ( ), HGIIN + Cl /SBA15 ( ), HGIIN + Cl /MCM41 ( ) and HGIIN + Cl /silica ( ). 6 C, catalyst 5 ppm, toluene, c 1 =.15 mol/l Figure S6. HM of methyl oleate with catalysts HGIIN + Cl ( ), HGIIN + Cl /SBA15 ( ), HGIIN + Cl /MCM41 ( ) and HGIIN + Cl /silica ( ). 6 C, catalyst 4 ppm, toluene, c 3 =.15 mol/l.

6 Split test for RCM of 1,7octadiene over HGIIN + Cl /SBA15 in toluene was performed as follows: after 5 minutes of the reaction, half of the liquid phase was filtered off at the reaction temperature and transferred into a parallel reactor, where it was kept under the same conditions as the parent reaction mixture in the original reactor. In the original reactor, reaction continued reaching nearly 1% of conversion, whereas in the reactor with separated liquid phase, the reaction stopped immediately. It indicates the solid catalyst is responsible for the catalytic activity in metathesis reactions studied Figure S7. Split test for RCM of 2; toluene, c 2 =.15 mol/l, 4 C, HGIIN + Cl /SBA15 4 ppm; suspension ( ), filtrate ( ).

7 Figure S8. Influence of SBA15 calcination temperature T = 3 C ( ), 5 C ( ) and 7 C ( ) on 1 conversions in RCM. HGIIN + Cl /SBA15, 5 ppm, toluene, 6 C, c 1=.15 mol/l Reusing of catalyst HGIIN + Cl /SBA15 was studied in RCM of ()βcitronellene. After 5 h of the reaction, the catalyst was separated by filtration, washed out with toluene and new portions of toluene, and ()βcitronellene were added. Table S3. Recovery and reuse of HGIIN + Cl /SBA15 in RCM of 1. Run a) (248) d) 97 (491) 94 (726) 9 (951) 47 (169) 99 b) (248) 97 (491) 96 (731) 95 (969) 79 (1167) 94 c ) (94) 79 (173) 38 (211) 8 (2118) 3 (2121) a 6 C, 5 h, catalyst.4 mol% (4 ppm), toluene, c 1 =.15 mol/l b 6 C, 5 h, catalyst.4 mol% (4 ppm), ethyl acetate, c 1 =.15 mol/l c 6 C, 5 h, catalyst.1 mol% (1 ppm), toluene, c 1 =.15 mol/l d cumulative TON is given in brackets

8 Figure S9. Influence of substrate concetration on conversion in RCM of 1; HGIIN + Cl /SBA15 5 ppm, toluene, 6 C, c 1 =.15 mol/l ( ), c 1 = 1 mol/l ( ) and neat substrate ( ). 1 TON = TON = Figure S1. RCM of 1 with HGIIN + Cl /SBA15 in neat substrate, 6 C, catalyst ppm: 168 ( ), 84 ( ), 42 ( ), 21 ( ). Activation energy E a was calculated from the ()βcitronellene TOF 5 values for the six temperatures. We plotted the ln TOF 5 as a function of 1/T for calculating the activation energy (Ea) of ()βcitronellene metathesis via an Arrhenius equation. From the slope of the resulting linear plot, we obtained E a = 31.1 kj/mol.

9 C E a = 31.6 KJ/mol ln TOF C 5 C 4 C 2 C /T (K) C Figure S11. Arrhenius plot effect of temperature on reaction rate in RCM of 1, HGIIN + Cl /SBA 15 5 ppm, toluene, c 1 =.15 mol/l Figure S12. Influence of solvent on conversion in RCM of 2; HGIIN + Cl /SBA15 4 ppm, c 2 =.15 mol/l, C; toluene ( ), CH 2 Cl 2 ( ), ethyl acetate ( ) and THF ( ).

10 Figure S13. Influence of solvent on conversion in HM of 3; HGIIN + Cl /SBA15 4 ppm, c 3 =.15 mol/l, 3 C; toluene ( ), CH 2 Cl 2 ( ), ethyl acetate ( ) and THF ( ). Appropriate amount of HGIIN + Cl /SBA15 (4 ppm) was dissolved in 1 ml of THF or CH 2 Cl 2. Prepared solution was mixed for 24 h at ambient temperature. After that solvent was filtered off, catalyst was dried in vacuum and used in RCM of 1 in toluene. Only 1 wt.% of initial amount of catalyst has been washed out from the support in both cases Figure S14. Activity of HGIIN + Cl /SBA15 ( ) and HGIIN + Cl /SBA15 washed with THF ( ), CH 2 Cl 2 ( ) in RCM of 1; 6 C, toluene, c 1 =.15 mol/l, HGIIN + Cl /SBA15 4 ppm. Maximum 1 wt.% of of initial amount of Ru alkylidene could be removed from the catalyst by washing with THF or CH 2 Cl 2.

11 Preparation of HGIIN + I Complex IV was prepared as described previously. 1 Complex IV (1. g, 1.33 mmol) was dissolved in AcOEt (1 ml) and methyl iodide (4.18 ml, 5 eq) was added. Reaction mixture was stirred at room temperature for 3 h, product precipitated during reaction course. HGIIN + I was filtered, washed with AcOEt (1 ml) and dried; green powder, 1.1g, 85%. 1 H NMR (6 MHz, CD 2 Cl 2 ) δ ppm: (s, 1H), (m, 1H), (m, 4H), (m, 2H) 6.88 (d, 1H, J=8.4Hz), 4.92 (heptet, 1H, J=6.Hz), 4.68 (pent, 1H, J=7.2Hz), 4.37 (pseudot, 1H, J=1.8Hz), 3.94 (pseudot, 1H, J=9.6Hz), (m, 2H, NCH 2 CH 3 ), (m, 2H), (m, 5H), (m, 4H), (m, 2H), 2.46 (bs, 18 H), 1.39 (t, 3H, J=6.6Hz, NCH 2 CH 3 ), 1.25 (d, 6H, J=6.Hz). 13 C NMR (75,4 MHz, CD 2 Cl 2 ) δ ppm: 296.5, 213.8, 152., 145.1, 139.1, 138.9, 131.9, 131.9, 129.9, 129.7, 129.4, 128.5, 128.4, 122.3, 122.2, 113., 75.2, 6.2, 6.2, 6.1, 46.7, 46.6, 2.9, 2.8, 2.8, 7.8. HRMS (ESI) calcd for C 39 H 55 N 4 OCl 2 Ru ([MI]+) m/z found H NMR spectrum of HGIIN + I

12 13 C NMR spectrum of HGIIN + I Preparation of HGIIN + PF 6 Commercially available HGIIN + Cl (5. g, 6.22 mmol) was dissolved in water (5 ml) and solution of ammonium hexafluorophosphate (2.3 g, 2 eq) in water (5 ml) was added. Precipitated light green solid was filtered, washed with water (1 ml) and dried on high vacuum at room temperature for 48 h; 5.34 g, 95%. 1 H NMR (6 MHz, CD 2 Cl 2 ) δ ppm: 16.4 (s, 1H), (m, 1H), (m, 4H), (m, 2H), 6.8 (d, 1H, J=8.4Hz), 4.83 (hept, 1H, J=6.Hz), (m, 1H), 4.23 (pseudot, 1H, J=1.8Hz), 3.85 (pseudot, 1H, J=1.2Hz), 3.24 (q, 2H, J=7.2Hz), (m, 4H), 2.86 (s, 3H), (m, 2H), (m, 4H), 2.38 (s, 18H), 1.27 (t, 3H, J=7.2Hz), (m, 6H). 13 C NMR (151 MHz, CD 2 Cl 2 ) δ ppm: 296.5, 213.7, 152., 145.1, 139.4, 139.1, 138.9, 129.7, 129.4, 122.4, 122.2, 113., 75.2, 6.6, 6.1, 6., 46.7, 46.6, 46.2, 2.9, 2.9, 2.8, P NMR (242.3 MHz CD 2 Cl 2 ) δ ppm: (heptet, 1P, J=1758 Hz). HRMS (ESI) calcd for C 39 H 55 N 4 OCl 2 Ru ([MPF 6 ]+) m/z found

13 1 H NMR spectrum of HGIIN + PF 6 13 C NMR spectrum of HGIIN + PF 6

14 31 P NMR spectrum of HGIIN + PF 6 Preparation of HGIIN + BF 4 HGIIN + BF 4 was prepared according to the procedure described for HGIIN + PF 6 with the use of ammonium tetrafluoroborate instead of ammonium hexafluorophosphate. Green solid was isolated in 9% of yield (4.79 g). 1 H NMR (6 MHz, CD 2 Cl 2 ) δ ppm: (s, 1H), (m, 1H), (m, 4H), (m, 2H), 6.86 (d, 1H, J=8.4Hz), 4.9 (hept, 1H, J=6.Hz), (m, 1H), 4.3 (pseudot, 1H, J=1.8Hz), 3.92 (pseudot, 1H, J=1.2Hz), 3.36 (q, 2H, J=7.2Hz), (m, 2H), (m, 2H), 2.97 (s, 3H), (m, 2H), (m, 4H), 2.44 (s, 18H), 1.33 (t, 3H, J=7.2Hz), (m, 6H). 13 C NMR (151 MHz, CD 2 Cl 2 ) δ ppm: 296.4, 218.6, 152., 145.1, 139.4, 139.1, 138.9, 129.7, 129.4, 122.4, 122.2, 113., 75.2, 6.6, 6.1, 59.8, 46.7, 46.5, 46.2, 2.9, 2.9, 2.8, B NMR (192.5 MHz, CD 2 Cl 2 ) δ ppm: HRMS (ESI) calcd for C 39 H 55 N 4 OCl 2 Ru ([MBF 4 ]+) m/z found

15 1 H NMR spectrum of HGIIN + BF 4 13 C NMR spectrum of HGIIN + BF 4

16 11 B NMR spectrum of HGIIN + BF 4

17 References 1 Skowerski, K.; Szczepaniak, G.; Wierzbicka, C.; Gułajski, Ł.; Bieniek, M.; Grela K. Catal. Sci. Technol., 212, 2,