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F. Meng, Y. Hervault, L. Norel, K. Costuas, C. Van-dyck et al., Chemical Science 2012, 3, 3113. minutes. Then, dichloromethane (20 mL) and triethylamine (0.30 mL, 1.90 mmol) were added on the solids. The reaction mixture was stirred for 2 days. Then, the solvents were removed under reduced pressure. The residue was taken up in dichloromethane (15 mL) and cannula transferred through a paper filter in an other schlenk. The first schlenk was rinced (2 × 15 mL) and further cannula transferred. The solution was concentrated, the schlenk tube was cooled down to -50 °C, and pentane (50 mL) was slowly added leading to the formation of an orange precipitate that was washed with pentane, × 15 mL). Complex 31 was obtained as a yellow powder, p.65

. Mhz, 6 (s, PPh 2 ) 13 C NMR (125.8 MHz, CD2Cl 2 , 297 K): ? 195

. Si, 159 g, 0.94 mmol) and (H3C)3Si?C?C?C6H5?C?C?H (0.070 g, 0.35 mmol) were dried under vacuum for 30 minutes. Then, well degassed dichloromethane (20 mL) and triethylamine (0.65 mL, 4.72 mmol) was added on the solids. The reaction mixture was stirred for 24 hours. Then solvent was removed under reduced pressure. The residue was taken up in THF (10 mL) and filtered. Then the solvent was removed under reduced pressure. The residue was taken up in CH2Cl2 (5 mL) and the solution was cooled down to -78°C. Pentane (35 mL) was slowly added leading to the formation of a yellow precipitate that was further washed with pentane, × 15 mL). 33 was obtained as a yellow solid (160 mg, 42%). 31 P NMR (81 MHz, CDCl3, 297 K): ? = 53.5 (s, PPh2). 1 H NMR, p.6

C. Mhz, 297 K): ? = 7, pp.60-66

C. Tms, 77 (d, 3 JH_H = 6.0 Hz, 2H, m-C6H4?p-SCOCH3 or m-C6H4?p-C?C?TMS), pp.62-248

C. Fab-+, 27 (s, ipso-C6H4?p-SCOCH3)30 (s, C?C?C6H4?p-SCOCH3) and 116.72 (s, C?C?C6H4?C?C? TMS), 106.21 (s, C6H4?C?C?TMS or C6H4?C?C?TMS), 93.58 (s, C6H4?C?C00 (s, COCH3) 0.0 (s, CH3Si) IR (KBr): ? (cm -1 ) = Elemental analysis (%) for C75H68OP4RuSSi, pp.7669-1704

C. Tms, 10 (s, 1H, 60 (m, 8H, PCH2CH2P), 2.41 (s, 3H, CH3). EXPERIMENTAL PART 249 trans-{(AcS?p?C?C)(dppe)2Ru}(µ-C?C?C6H4?CH=CH)?{RuCl(CO)(P i Pr3)2} (35) Ru P i Pr 3

C. Sac, 7 and the diethynyl-substituted dithienylethene, 1 were prepared as previously reported . * : reaction carried under dark conditions, trans-[(dppe)2Ru(Cl), pp.6-10

R. Cl and O. , 200 g, 0.16 mmol) was dried under vacuum for 30 minutes. Then, well degassed dichloromethane (20 mL) was added on the solids Then triethylamine (0.40 mL, 3.18 mmol) was added dropwise on the solution. The reaction mixture was stirred for 30 minutes. The organic layer was washed with water (3 × 10 mL) The remaining solvent was removed under reduced pressure. The residue was taken up in THF (10 mL) and filtered. The solvent were removed under reduced pressure, and the residue was taken up in CH2Cl2 (5 mL) and the solution was cooled down to -78°C, Pentane (35 mL) was slowly added, leading to the formation of a yellow precipitate that was further washed with pentane

C. Mhz, 97 (s, C=O), 155.21 (p-C6H4?p-O), 136.79 and 135, pp.36-128

C. Fab-+, 63 (s, m-C6H4?p-O) 112.69 (s, Ru?C?C? C6H5)72 (s, O?CH2) 30.74 (m, | 1 JPC + 3 JPC| = 23 Hz, CH2), 30.46 (s, CH3), 29.50 (s, CH2), 29.31 (s, CH2), 29.07 (s, CH2), 28.60 (s, CH2), 25.70 (s, CH2) IR (KBr): ? (cm -1 ) =, .2538). Elemental analysis (%) for C68H67ClO2P4RuS: C 66.95, pp.30-1690

. Duced-pressure, The residue was taken up in CH2Cl2 (5.0 mL) and the solution was cooled down to -78°C. Then pentane (35 mL) was slowly added leading to the formation of a yellow precipitate. that was further washed with pentane (2 × 15 mL). 14 was obtain as a yellow solid, p.82

C. Mhz and H. Fab-+, 85 (s, o-C6H4?p-O), 130.73 (s, ipso-C6H5), 129.99 (s, o-C6H5), 128.50 (s, 116.46 and 115.66 (s, Ru-C?C? C6H5) JPC + 3 JPC| = 23 Hz, CH2), 30.66 (s, CH3), 29.51 (s, CH2) CH2). IR (KBr): ? (cm -1 ) = 1688 (C=O), pp.196-197