SUPPORTING INFORMATION FOR:

Transcription

1 SUPPORTING INFORMATION FOR: A New Ru Complex Capable of Catalytically Oxidize Water to Molecular Dioxygen Cristina Sens, Isabel Romero, Montserrat Rodríguez and Antoni Llobet,* Teodor Parella and Jordi Benet-Buchholz # Departament de Química, Universitat de Girona, Campus de Montilivi, E Girona, Spain. E- mail: antoni.llobet@udg.es. Servei de RMN, Universitat Autònoma de Barcelona, Bellaterra, E Barcelona, Spain. # BIS-ZAS X-ray Laboratory, Geb. Q18; Raum 490, Bayer AG, D Leverkusen, Germany and Institut Català d'investigació Química (ICIQ) Avgda. Països Catalans, s/n, Tarragona, Spain S1

2 - Cif magnetic files attached separately - Scheme S1. Synthetic pathway - Details for synthetic procedure and redox properties of compounds 1 and 2. - Acid-base spectrophotometric titration details - Figure S1. Ortep plot (ellipsoids at 40% probability) X-ray structure of the cationic moiety of [Ru 2 II(µ-Cl)(bpp)(trpy) 2 ] 2+, 1, together with labeling scheme. - Figure S2. 1D and 2D NMR spectra (500 MHz, 298 K, acetona-d 6 ) for complex 1: (a) 1 H-NMR, (b) COSY, (c) NOESY, (d) 1 H- 13 C correlation and (e) 13 C-NMR. - Figure S3. 1D and 2D NMR spectra (500 MHz, 298 K, acetona-d 6 ) for complex 2: (a) 1 H-NMR, (b) COSY, (c) COSY, aromatic region, (d) NOESY, (e) 1 H- 13 C correlation and (f) 1 H- 13 C correlation aromatic region. - Figure S4. 1D and 2D NMR spectra (500 MHz, 298 K, D 2 O with a drop of trifluoroacetic acid) for complex 3: (a) 1 H-NMR, (b) COSY, (c) NOESY and (d) 1 H- 13 C correlation aromatic region. - Figure S5. UV-Vis spectroscopy of the different species generated upon oxidation of 3 with Ce(IV) in 0.1 M CF 3 COOH. - Figure S6. Cyclic voltammogram of 3 at ph = 1 in CF 3 COOH at a scan rate of 100 mv/s vs. SSCE using a glassy carbon electrode. - Figure S7. Oxygen evolution measured with a GC from the reaction of 3 and excess Ce(IV) (see text for details). The inset shows plots of initial O 2 evolution rates, V O2 (mols s -1 ) vs. complex concentration in an aqueous 0.1 M CF 3 SO 3 H solution (y = x x 10-9 ); Ce(IV), 5.25 x 10-4 mols in 2 ml total volume. - Table S1. 1 H-NMR assignment for 1, 2 and 3. - Table S2. UV-Vis features of 3 and their higher oxidation state species. S2

3 Scheme S1. i) LiCl, NEt 3 ii) bpp - 2 [Ru III Cl 3 (trpy)] iii) NaOAc PF6 - [Ru II 2 (µ-cl)(bpp)(trpy)2 ](PF6)2 4h reflux in MeOH 2h reflux in water: [Ru II 2 (µ-oac)(bpp)(trpy)2 ](PF6)2 acetone (1:3) 1 2 Synthetic details. Synthesis of 1 0.5H 2 O. A sample of g (1.174 mmol) of RuCl 3 (trpy) and g (3.522 mmol) of LiCl were dissolved in 40 ml of MeOH containing 327 µl (2.351 mmol) of NEt 3, used as reducing agent. The mixture is then stirred at RT for 20 minutes and then 10 ml of MeOH containing g (0.587 mols) of Hbpp and g (0.589 mols) of NaMeO is added. The resulting mixture is heated at reflux for 4 h. The solution is then filtered and the volume reduced to dryness. The product is purified by column chromatography using alumina as the solid support and CH 2 Cl 2 and acetone as elutants. The product thus obtained is finally recrystallized from a mixture of acetone:water. Yield: g (73.4 %). Anal. Calcd. for C 43 H 31 Cl 1 F 12 N 10 P 2 Ru 2 0.5H 2 O: C, 42.18; H, 2.63; N, Found: C, 42.35; H, 2.76; N, Synthesis of 2. A sample of g (0.092 mmol) of 1 0.5H 2 O and g (0.464 mmol) of sodium acetate were dissolved in 20 ml acetone:water (3:1) and heated at reflux for 2h. The resulting solution is filtered and a few drops of saturated solution of NaPF 6 added. Upon reducing the volume a solid comes out of the solution that is washed with cold water and ether. Yield: g (78.9 %). Anal. Calcd. for C 45 H 34 F 12 N 10 O 2 P 2 Ru 2 : C, 43.63; H, 2.77; N, Found: C, 43.74; H, 2.96; N, Details of the acid-base spectrophotometric titration of 3. For the acid-base spectrophotometric titration, a M aqueous solution of 2 in CF 3 COOH was used (25 ml). The ph of the solution was adjusted by adding small volumes (approx. 10 µl) of 4 M NaOH. Chemically reversible redox processes observed at ph = 1 (global complex charges and ligands, except for the aqua, have been omitted for clarity purposes): E 1/2 = V vs. SSCE, at ph = 1.0 E 1/2 = V vs. SSCE, at ph = 1.0 E 1/2 = V vs. SSCE, at ph = 1.0 S3

4 Figure S1. C10 C9 C11 C8 C2 C3 C12 C4 N3 C5 C6 C7 C15 C14 C16 C1 C17 C18 N1 N4 N5 Ru1 C22 N2 Cl1 C19 C21 C20 S4

5 Figure S2. (a) S5

6 (b) S6

7 (c) S7

8 (d) S8

9 (e) S9

10 Figure S3. (a) ppm ppm S10

11 (b) ppm ppm S11

12 (c) ppm ppm S12

13 (d) ppm ppm S13

14 (e) ppm ppm S14

15 (f) ppm ppm S15

16 Figure S4. (a) B) ppm S16

17 (b) ppm ppm S17

18 (c) (ppm) (ppm) S18

19 (d) ppm ppm S19

20 Figure S Absorbance III-III II-II II-III 0 III-IV wavelength (nm) Ru II -Ru II stands for [Ru 2 II,II (bpp)(trpy) 2 (OH 2 ) 2 ] 3+ ; Ru II -Ru III for [Ru 2 II,III (bpp)(trpy) 2 (OH 2 ) 2 ] 4+ ; Ru III -Ru III for [Ru 2 III,III (bpp)(oh)(trpy) 2 (OH 2 )] 4+ ; Ru III -Ru IV for [Ru 2 III,IV (bpp)(oh) 2 (trpy) 2 ] 4+. S20

21 Figure S6. 8.E-06 6.E-06 4.E-06 I (A) 2.E-06 0.E+00-2.E-06-4.E E (V) S21

22 Figure S mol O Vo mol s [complex] 10-3 (M) t (h) S22

23 Table S1. Complex a 1 1 H-RMN (500 MHz, acetona-d 6 ): δ 8.68 (d, 3 J = 3 J = 8 Hz, H14, H16), 8.54 (dd, 3 J = 3 J = Hz, 4 J 11-9 = 4 J = 1.4 Hz, H11, H19), 8.52 (s, H7), 8.40 (dd, 3 J 8-9 = 3 J = 5.6 Hz, 4 J 8-10 = 4 J = 1.4 Hz, H8, H22), 8.27 (ddd, 3 J 4-3 = 8.05 Hz, 4 J 4-2 = 1.4 Hz, 5 J 4-1 = 0.7 Hz, H4), 8.16 (t, 3 J = 3 J = 8 Hz, H15), 7.96 (td, 3 J 10-9 = 3 J = 3 J = 3 J = Hz, 4 J 10-8 = 4 J = 1.4 Hz, H10, H20), 7.83 (td, 3 J 3-2 = 3 J 3-4 = 8.05 Hz, 4 J 3-1 = 1.4 Hz, H3), 7.63 (ddd, 3 J 9-10 = 3 J = Hz, 3 J 9-8 = 3 J = 5.6 Hz, 4 J 9-11 = 4 J = 1.4 Hz, H9, H21), 7.46 (ddd, 3 J 1-2 = 5.8 Hz, 4 J 1-3 = 1.4 Hz, 5 J 1-4 = 0.7 Hz, H1), 6.82 (ddd, 3 J 2-3 = 8.05 Hz, 4 J 2-1 = 5.8 Hz, 4 J 2-4 = 1.4 Hz, H2). 2 1 H-RMN (500 MHz, acetona-d 6 ): δ 8.74 (d, 3 J = 3 J = 3 J = 3 J = 8.25 Hz, H20, H22, H35, H37), 8.62 (d, 3 J = 3 J = 3 J = 3 J = 8.05 Hz, H17, H25, H32, H40), 8.58 (s, H7), 8.45 (d, 3 J = 3 J = 3 J = 3 J = 5.25 Hz, H14, H28, H29, H43), 8.23 (d, 3 J 4-3 = 3 J = 7.85 Hz, H4, H10), 8.18 (t, 3 J = 3 J = 3 J = 3 J = 8.05 Hz, H21, H36), 8.02 (t, 3 J = 3 J = 3 J = 3 J = 8.05 Hz, 3 J = 3 J = 3 J = 3 J = 7.7 Hz, H16, H26, H31, H41), 7.73 (t, 3 J 3-2 = 3 J = 7.55 Hz, 3 J 3-4 = 3 J = 7.85 Hz, H3, H11), 7.53 (t, 3 J = 3 J = 3 J = 3 J = 5.25 Hz, 3 J = 3 J = 3 J = 3 J = 7.7 Hz, H15, H27, H30, H42), 6.83 (t, 3 J 2-1 = 3 J = 5.75 Hz, 3 J 2-3 = 3 J = 7.55 Hz, H2, H12), 0.42 (s, acetate) 3 1 H-RMN (500 MHz, D 2 O/ a drop of CF 3 COOH): δ 8.63 (d, 3 J = 3 J = 3 J = 3 J = 8.1 Hz, H20, H22, H35, H37), 8.52 (d, 3 J = 3 J = 3 J = 3 J = 8.15 Hz, H17, H25, H32, H40), 8.44 (s, H7), 8.39 (dd, 3 J = 3 J = 3 J = 3 J = 5.35 Hz, 4 J = 4 J = 4 J = 3 J = 1.35 Hz, H14, H28, H29, H43), 8.18 (t, 3 J = 3 J = 3 J = 3 J = 8.1 Hz, H21, H36), 8.17 (dd, 3 J 4-3 = 3 J = 7.9 Hz, 4 J 4-2 = 4 J = 1.05 Hz, H4, H10), 7.98 (ddd, 3 J = 3 J = 3 J = 3 J = 8.15 Hz, 3 J = 3 J = 3 J = 3 J = Hz, 4 J = 4 J = 4 J = 4 J = 1.35 Hz H16, H26, H31, H41), 7.70 (ddd, 3 J 3-2 = 3 J = 7.7 Hz, 3 J 3-4 = 3 J = 7.9 Hz, 4 J 3-1 = 4 J = 1.25 Hz, H3, H11), 7.51 (dd, 3 J = 3 J = 3 J = 3 J = 5.35 Hz, 3 J = 3 J = 3 J = 3 J = Hz, H15, H27, H30, H42), 7.42 (dd, 3 J 1-2 = 3 J = 5.6 Hz, 4 J 1-3 = 4 J = 1.25 Hz, H1, H13), 6.79 (ddd, 3 J 2-1 = 3 J = 5.6 Hz 3, J 2-3 = 3 J = 7.7 Hz, 4 J 2-4 = 4 J = 1.05 Hz, H2, H12) a the labels used here for the resonances are those of the x-ray structure shown in Figure 1 and S1. For 3, we have used the same labeling scheme as for complex 2. S23

24 Table S2. Complex λ max, nm (ε, M -1 cm -1 ) II,II [Ru 2 (bpp)(trpy) 2 (OH 2 ) 2 ] (56559), 314(57661), 471(11882), 354(20322), 490(11021) II,III [Ru 2 (bpp)(trpy) 2 (OH 2 ) 2 ] (52204), 312(47769), 464(9113) sh at 359 wide band centered at 574 III,III [Ru 2 (bpp)(oh)(trpy) 2 (OH 2 )] (49758), 312(46129) sh at 452 wide band centered at 547 [Ru 2 III,IV (bpp)(oh) 2 (trpy) 2 ] (47769), 313(46290) wide band centered at 501 S24