Synthesis and Application of Stereoretentive Ruthenium Catalysts on the Basis of the M7 and the Ru-Benzylidene- Oxazinone Designs

Transcription

1 ynthesis and Application of tereoretentive Ruthenium Catalysts on the Basis of the M7 and the Ru-Benzylidene- xazinone Designs Adrien Dumas,, Daniel. Müller, Idriss Curbet, Loïc Toupet, Matthieu Rouen, livier Baslé,*, and Marc Mauduit*, Univ Rennes, Ecole Nationale upérieure de Chimie de Rennes, CNR, ICR UMR 6226, F Rennes, France Institut de Physique de Rennes, Université Rennes 1, CNR UMR 6251, 263 Av. Général Leclerc, Rennes, France DEMETA A, 6 rue Pierre-Joseph Colin, Rennes, France for M.M.: for.b.: marc.mauduit@ensc-rennes.fr. olivier.basle@ensc-rennes.fr. 1

2 Table of contents General page 3 Preparation of Ru-complexes page 4 Explanation concerning the two observed diastereoisomers page 8 tability of synthesized Ru-catalysts in THF at 60 C page 9 General procedure for the Ring pening Cross Metathesis (RCM) page 10 General procedure for Cross Metathesis (CM) reactions page 11 Procedure for the synthesis of Yuzu lactone page 29 Procedure for cross metathesis of methyl 9-octadecenoate experiments page 34 Procedure for catalyst initiation experiments page 39 X-Ray structures of Ru-7 and Ru-8 page 41 References page 56 NMR spectra page 57 2

3 General 1 H (400 MHz) and 13 C (101 MHz) NMR spectra were recorded on a Bruker 400 NMR spectrometer with complete proton decoupling for nucleus other than 1 H. Chemical shifts are reported in parts per million with the solvent resonance as the internal standard (CDCl 3 : 1 H, δ 7.26 ppm; 13 C, δ ppm; CD 2 Cl 2 : 1 H, δ 5.30 ppm; 13C, δ ppm). Coupling constants (J) are reported in hertz (Hz). Multiplicities are reported using the following abbreviations: s = singlet, br s = broad singlet, d = doublet, dd = double doublet, ddd = double double doublet, dt = double triplet, t = triplet, td = triple doublet, q = quartet, quint = quintet, sept = septet, m = multiplet. High Resolution Mass pectrometry (HRM) analysis were performed at the Centre Régional de Mesures Physiques de l uest (CRMP), Université de Rennes 1, on a Q- Exactive apparatus in EI mode. Dichloromethane and tetrahydrofuran were purified using MBraun MB-P-5 olvent Purification ystem. All solvents and deuterated solvents were degassed unless otherwise noted. Materials and Methods. Unless otherwise specified, all reactions were carried out under airfree conditions in dry glassware in a MBraun glovebox filled with argon. Dichloromethane and tetrahydrofuran were purified using MBraun MB-P-5 olvent Purification ystem. Pentane, C 6 D 6 and CD 2 Cl 2, THF-d 8 were distilled over calcium hydride or sodium under Ar. All solvents and deuterated solvents were degassed unless otherwise noted. All olefin substrates were dried over basic alumina, distilled and degassed by three freeze-pump-thaw cycles prior to use. Reactions were monitored by thin-layer chromatography (TLC) carried out on silica gel plates (60F254) using UV light as visualizing agent and by staining with KMn 4. Column chromatography was performed with silica gel (spherical, particle size 40 μm, neutral). olvents used for catalysis products purifications were used as received. CDCl 3, CD 2 Cl 2, THF-d 8 were purchased from Euriso-Top company. Ru-catalysts precursors for the synthesis of Ru-6, [1] Ru-7, [1] Ru-8, [2] Ru-9 [2] and Ru-10 [2] were synthesized as previously described or obtained from DEMETA.A.. Ru-1 and Ru-4 were synthesized from Hoveyda-Grubbs 2nd generation (CA: ) catalyst and Grubbs catalyst C711 (CA: ) respectively. Zinc 3,6-dichlorobenzene-1,2-dithiolate salt [3] and (but-3- enyloxy)(tert-butyl)dimethylsilane [4] were prepared according to literature. All other chemicals or reagents were obtained from commercial sources. 3

4 Preparation of Ruthenium complexes Preparation of complex Ru-6 Cl N N Ru i Bu N Cl i H Pr Ru-6: C 42 H 49 Cl 2 N 3 3 Ru 2 MW: In a glovebox, a chlenk flask equipped with a magnetic stir bar was charged with the dichloro ruthenium complex precursor of Ru-6 (150.0 mg, mmol, 1.0 equiv) and THF (2.5 ml). Zinc 3,6-dichlorobenzene-1,2-dithiolate salt (111.0 mg, mmol, 2.0 equiv) was added and the resulting mixture was allowed to stir at rt for 2 h, at which time the solvent was evaporated under vacuum. The crude residue was then taken up in dichloromethane and passed through a short column of celite. The filtrate was concentrated and dichloromethane was co-evaporated with pentane to afford Ru-6 as a yellow-brown solid (170 mg, 96%). 1 H NMR (400 MHz, CD 2 Cl 2 ): (s, 1H), (m, 1H), 7.06 (d, J = 8.9 Hz, 1H), 6.96 (br s, 2H), 6.89 (d, J = 8.1 Hz, 1H), 6.80 (d, J = 8.1 Hz, 1H), (m, 3H), 6.27 (br s, 1H), (m, 1H), (m, 6H), 2.52 (br s, 6H), (m, 9H), 1.96 (sept, J = 6.8 Hz, 1H), (m, 6H), 1.47 (d, J = 6.6 Hz, 3H), 0.97 (d, J = 6.7 Hz, 6H). 13 C NMR (101 MHz, CD 2 Cl 2 ): 252.3, 252.0, 217.4, 154.1, 150.5, 142.2, 142.1, 139.0, 136.6, 133.8, 131.5, 129.9, 129.8, 129.6, 123.4, 121.9, 117.6, 116.1, 114.1, 82.6, 71.8, 51.9, 28.6, 24.6, 21.5, 21.1, HRM: [M] +. calcd for C 42 H 49 N Cl Ru, ; found, Preparation of Complex Ru-7. Cl N N Ru i Bu N i Pr H Cl Ru-7: C 48 H 61 Cl 2 N 3 3 Ru 2 MW: In a glovebox, a chlenk flask equipped with a magnetic stir bar was charged with the dichloro ruthenium complex precursor of Ru-7 (500 mg, mmol, 1.0 equiv) and THF (7.5 ml). Zinc 3,6-dichlorobenzene-1,2-dithiolate salt (332 mg, 1.21 mmol, 2.0 equiv) was added and the resulting mixture was allowed to stir at rt for 5 h, at which time the solvent was evaporated under vacuum. The crude residue was then taken up in dichloromethane and passed through a short column of celite. The filtrate was concentrated and dichloromethane was co-evaporated with pentane to afford Ru-7 as a yellow-brown solid (581 mg, 99%). 4

5 1 H NMR (400 MHz, CD 2 Cl 2 ): (s, 1H), (m, 1H), (m, 3H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), 6.51 (s, 1H), 6.40 (d, J = 2.7 Hz, 1H), 4.91 (sept, J = 6.2 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 5H), (m, 1H), (m, 1H), 1.97 (sept, J = 6.7 Hz, 1H), 1.90 (d, J = 6.3 Hz, 3H), 1.40 (d, J = 5.9 Hz, 3H), 1.36 (d, J = 6.8 Hz, 3H), (m, 6H), (m, 6H), (m, 9H), 0.52 (d, J = 6.6 Hz, 3H), 0.14 (d, J = 6.6 Hz, 3H). 13 C NMR (101 MHz, CD 2 Cl 2 ): 259.1, 259.0, 220.3, 154.3, 153.7, 151.9, 149.6, 148.9, 147.3, 145.8, 143.1, 142.0, 138.8, 136.0, 133.5, 131.5, 130.6, 130.1, 129.4, 126.0, 125.9, 125.6, 124.5, 123.5, 122.0, 119.2, 115.4, 115.0, 76.8, 71.8, 54.5, 54.4, 30.1, 29.5, 29.2, 28.9, 28.6, 27.5, 27.4, 26.8, 26.1, 26.0, 24.1, 23.4, 21.9, 21.2, 20.7, HRM: [M] +. calcd for C 48 H 61 N Cl Ru, ; found, Preparation of Complex Ru-8. Cl Cl N Ru N NH C 43 H 49 Cl 2 N 3 2 Ru 2 Ru-8: MW: 875,97 In a glovebox, a chlenk flask equipped with a magnetic stir bar was charged with the dichloro ruthenium complex precursor of Ru-8 (44.9 mg, mmol, 1.0 equiv) and THF (1.3 ml). Zinc 3,6-dichlorobenzene-1,2-dithiolate salt (32.9 mg, 0.12 mmol, 2.0 equiv) was added and the resulting mixture was allowed to stir at rt for 2 h, at which time the solvent was evaporated under vacuum. The crude residue was then taken up in dichloromethane and passed through a short column of celite. The filtrate was concentrated and dichloromethane was coevaporated with pentane to afford Ru-8 as a yellow-brown solid (49.3 mg, 93%). Two diastereomers were observed; d.r. = 89:11. The most abundant is described. 1 H NMR (400 MHz, CD 2 Cl 2 ): (s, 1H), 7.87 (br s, 1H), (m, 2H), 7.35 (q, J = 7.6 Hz, 2H), (m, 1H), (m, 5H), 6.32 (dd, J = 7.0, 2.1 Hz, 1H), 4.88 (q, J = 6.8 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 1.91 (d, J = 6.4 Hz, 3H), 1.38 (d, J = 6.7 Hz, 3H), 1.30 (d, J = 6.9 Hz, 3H), 1.26 (d, J = 6.8 Hz, 6H), 1.07 (d, J = 6.8 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 0.52 (d, J = 6.6 Hz, 3H), 0.12 (d, J = 6.6 Hz, 3H). 13 C NMR (101 MHz, CD 2 Cl 2 ): 257.5, 219.5, 167.1, 153.9, 149.4, 148.7, 147.2, 145.4, 144.4, 141.6, 141.2, 138.6, 135.0, 131.4, 130.7, 130.3, 129.2, 128.0, 126.2, 125.9, 125.8, 125.5, 124.4, 123.7, 122.1, 118.3, 114.7, 78.4, 30.0, 29.4, 29.0, 28.9, 27.5, 27.3, 27.2, 26.4, 26.2, 25.7, 24.1, 21.8, 20.0, HRM: [M] +. calcd for C 43 H 49 N Cl Ru, ; found,

6 Preparation of Complex Ru-9. Cl Cl N Ru N In a glovebox, a chlenk flask equipped with a magnetic stir bar was charged with the dichloro ruthenium complex precursor of Ru-9 (44.0 mg, mmol, 1.0 equiv) and THF (830 L). Zinc 3,6-dichlorobenzene-1,2-dithiolate salt (36.2 mg, mmol, 2.0 equiv) was added and the resulting mixture was allowed to stir at rt for 2 h, at which time the solvent was evaporated under vacuum. The crude residue was then taken up in dichloromethane and passed through a short column of celite. The filtrate was concentrated and dichloromethane was co-evaporated with pentane to afford Ru-9 as a yellow-brown solid (53.2 mg, 99%). NH Ru-9: C 38 H 39 Cl 2 N 3 2 Ru 2 MW: Two diastereomers were observed; d.r. = 86:14. The most abundant is described. 1 H NMR (400 MHz, CD 2 Cl 2 ): (s, 1H), 7.81 (br s, 1H), (m, 2H), (m, 4H), (m, 1H), 6.51 (d, J = 7.1 Hz, 1H), (m, 1H), 4.59 (dd, J = 10.5, 3.7 Hz, 1H), 3.95 (br s, 4H), (m, 12H), (m, 11H). Ru-9 suffered from decomposition during the NMR experiment to acquire the 13 C-spectrum. Therefore only characteristic signals are given. 13 C NMR (101 MHz, CD 2 Cl 2 ): 249.3, 215.6, 164.5, 153.3, 142.4, 139.6, 136.1, 131.6, 129.9, 129.8, 85.3, 30.1, 24.5, 21.2, Preparation of Complex Ru-10. Cl Cl N Ru N NH Ru-10: C 44 H 51 Cl 2 N 3 2 Ru 2 MW: In a glovebox, a chlenk flask equipped with a magnetic stir bar was charged with the dichloro ruthenium complex precursor of Ru-10 (41.6 mg, mmol, 1.0 equiv) and THF (830 L). Zinc 3,6-dichlorobenzene-1,2-dithiolate salt (30.2 mg, 0.11 mmol, 2.0 equiv) was added and the resulting mixture was allowed to stir at rt for 2 h, at which time the solvent is evaporated under vacuum. The crude residue was then taken up in dichloromethane and passed through a short column of celite. The filtrate was concentrated and dichloromethane was co-evaporated with pentane to afford Ru-10 as a yellow-brown solid (48.4 mg, 98%) Two diastereomers were observed; d.r. = 84:16. The most abundant is described. 1 H NMR (400 MHz, CD 2 Cl 2 ): (s, 1H), 7.70 (s, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 5H), 6.31 (dd, J = 6.5 Hz, 2.5 Hz, 1H), 4.47 (d, 6

7 J = 10.6 Hz, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 1.91 (d, J = 6.5 Hz, 3H), (m, 2H), 1.38 (d, J = 6.1 Hz, 3H), (m, 9H), 1.07 (d, J = 6.8 Hz, 3H), 0.96 (d, J = 6.5 Hz, 3H), 0.50 (d, J = 6.6 Hz, 3H), 0.11 (d, J = 6.7 Hz, 3H) 13 C NMR (101 MHz, CD 2 Cl 2 ): 257.1, 256.8, 219.6, 167.4, 153.9, 149.5, 148.7, 147.3, 145.3, 144.5, 141.8, 141.2, 138.5, 134.8, 131.5, 130.3, 130.3, 129.1, 127.8, 126.2, 125.8, 125.6, 125.5, 124.3, 123.7, 122.0, 118.2, 114.8, 82.3, 30.1, 29.9, 29.3, 29.0, 28.9, 27.5, 27.1, 27.0, 26.3, 26.2, 25.7, 24.1, 21.7, 20.0, HRM: [M] +. calcd for C 44 H 51 N Cl Ru, ; found,

8 Explanation concerning the two observed diastereoisomers X-ray analysis of a single crystal of ruthenium complex Ru-8 identified a pair of enantiomers present in the crystal lattice ( - and -R). The observed diastereomer is shown in the upper part of Figure 1. Me H NHC C Ru - NHC Ru C -R H Me H Me C -R NHC Ru NHC Ru C - H Me Figure 1. X-Ray of ( - and -R) and structure of the corresponding molecules as well as its diastereomeric form. Note: The most abundant diastereomers for complexes Ru-8, Ru-9 and Ru-10 were not assigned. Concerning the nomenclature of chiral metal complexes see: tereochemistry of coordination compounds, Alexander von Zelewsky John Wiley & ons Ltd,

9 tability of synthesized Ru-catalysts in THF at 60 C In a glovebox a NMR tube was charged with Ru complex (0.005 mmol), anthracene (0.005 mmol) as the internal standard, and THF-d 8 (0.5 ml). The tube was sealed and shaken vigorously. A 1 H NMR spectrum was recorded for reference at time = 0. The tube was then placed in an oil bath set at 60 C. Degradation was monitored by observing the disappearance of the benzylidene signal by 1 H-NMR. 100% Remaining precatalyst (%) 80% 60% 40% 20% Ru-1 Ru-4 Ru-6 Ru-7 Ru-8 Ru-10 0% Times (h) Figure 2. Thermal stability study. 9

10 General procedure for the Ring pening Cross Metathesis (RCM) of norbornene and styrene. Exemplified for Ru-6. ((Z)-2-((1R,3)-3-vinylcyclopentyl)vinyl)benzene (3). 3: C 15 H 18 MW: In a glovebox, a stock solution of Ru-6 (8.0 mg, 6.8 mol, 1 mol%) in THF (500 L) was freshly prepared. A vial was charged with norbornene (15.0 mg, mmol, 1.0 equiv), styrene (0.364 L, 331 mg, 3.18 mmol, 20.0 equiv) and THF (230 L). Ru-6 stock solution (87.4 L, 1.59 mol, 1 mol%) was added to the vial and the resulting mixture was allowed to stir at rt for 1 hour. The reaction was quenched upon addition of wet diethyl ether. After complete evaporation of the solvents, tetrachloroethane (13.3 mg, mmol, 0.5 equiv) was added to the crude mixture. A 1 H NMR spectrum was recorded in CDCl 3 to calculate the conversion and NMR yield. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane) to yield 3 (29.3 mg, 93%) as a colorless oil. R f = 0.90 (pentane 100%); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): (m, 2H), (m, 3H), 6.38 (d, J = 11.5 Hz, 1H), 5.84 (ddd, J = 17.4, 10.2, 7.4 Hz, 1H), 5.60 (dd, J = 11.5, 10.0 Hz, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H). 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): 143.2, 138.1, 138.0, 128.7, 128.3, 127.7, 126.6, 112.7, 44.7, 41.6, 38.8, 33.2, Analytical data for this compound were consistent with previously reported data. [5] 10

11 Figure 3. Determination of Z/E ratio of compound 3 by 1 H-NMR analysis. General procedure for Cross Metathesis (CM) reactions with cis-2-butene-1,4-diol or cis-diacetoxy-2-butene exemplified for the synthesis of (Z)-tridec-2-en-1-ol (6): (Z)-tridec-2-en-1-ol (6) 6: C 13 H 26 MW: H In a glovebox, a stock solution of ruthenium catalyst Ru-6 (10.0 mg, 11.3 μmol) in THF (1.00 ml) was freshly prepared. An oven-dried 4 ml vial was charged with dodec-1-ene (16.8 mg, 0.10 mmol, 1.0 equiv.), cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv.) and THF (100 L). Then 442 L (5.0 μmol, 5.0 mol%) of Ru-6 stock solution was added to the previously prepared solution of olefin and cis-2-butene-1,4-diol and the mixture was allowed to stir for 4 hours at 22 C. The reactions were then quenched by addition of Et 2 (0.5 ml, technical grade) and the crude reaction mixture was analyzed by 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard, 80 % consumption of dodec-1-ene was observed. After evaporation of the solvents the dark suspension was dissolved in a minimum amount of acetone (~ 0.2 ml) and purified by silica 11

12 gel chromatography (Pentane:Et 2 = 5:1) and filtered through a small plug of activated charcoal to yield 6 (15.1 mg, 76 %) as a colorless oil in 98:2 Z/E ratio. Note 1: We were unable to determine the Z/E ratio from unpurified samples due to peak overlapping. The E/Z-ratio was determined on the combination of all obtained fractions containing product (The R f values of the E- and Z-isomers obtained in this study are almost identical). Note 2: Before column chromatographic purification it is important to dissolve the crude mixture in the minimum amount of acetone to give a homogenous solution. The column was then directly loaded with this solution. Using non polar solvents to load the column can lead to significant drops in yields due to the poor solubility in such solvent mixtures. This effect is particularly pronounced for very polar compounds such as 12, 13 and 14. Note 3: We noted severe isomerization of the obtained products (up to 50:50 mixtures of E/Zisomers) when the dry crude reaction mixtures were allowed to stand at room temperature for several days! This can be avoided by storing the crude reaction mixtures as solutions at 20 C or keeping the time between reaction and purification short (< 5 hours). R f = 0.40 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 2H), 4.18 (d, J = 6.1 Hz, 2H), 2.05 (td, J = 6.9, 6.9 Hz, 2H), (m, 16H), 0.87 (t, J = 6.9 Hz, 3H); H not seen due to D-H exchange; 13 C NMR (101 MHz, CDCl 3 ), Z- isomer (major): δ 133.3, 128.4, 58.7, 32.0, 29.7 (3 C), 29.6, 29.5, 29.4, 27.6, 22.8, Analytical data for this compound were consistent with previously reported data. [6] 12

13 Figure 4. Determination of Z/E ratio of compound 6 by 1 H-NMR analysis. (Z)-4-phenylbut-2-en-1-ol (9) 9: C 10 H 12 MW: H Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with allylbenzene (11.8 mg, 0.1 mmol, 1.0 equiv) and cis- 2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 78 % consumption of allylbenzene. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 5:1 to pentane:et 2 = 3:1) and filtered through a small plug of activated charcoal to yield 9 (5.9 mg, 40 %) as a pale yellow oil in 98:2 Z/E ratio. R f = 0.32 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 2H), (m, 3H), (m, 2H), (m, 2H), (m, 2H); H not seen due to D-H exchange: 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 140.3, 131.2, 129.4, 128.7, 128.4, 126.3, 58.7, Analytical data for this compound were consistent with previously reported data. [7] 13

14 Figure 5. Determination of Z/E ratio of compound 9 by 1 H-NMR analysis. 14

15 (Z)-5-(tert-butyldimethylsilyloxy)pent-2-en-1-ol (10) TB 10: C 11 H 24 2 i MW: H Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial to a vial charged with (but-3-enyloxy)(tert-butyl)dimethylsilane (18.6 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 67 % consumption of (but-3-enyloxy)(tert-butyl)dimethylsilane. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 5:1) and filtered through a small plug of activated charcoal to yield 10 (13.8 mg, 64%) as a colorless oil in 97:3 Z/E ratio. R f = 0.44 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 1H), 5.56 (dt, J = 10.9, 7.8 Hz, 1H), 4.12 (d, J = 6.7 Hz, 2H), 3.63 (t, J = 6.2 Hz, 2H), 2.32 (td, J = 7.5, 1.2 Hz, 3H; overlapping with RH), 0.88 (s, 9H), 0.04 (s, 6H); 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 131.0, 129.8, 62.4, 58.1, 31.0, 26.1, 18.6, Analytical data for this compound was consistent with previously reported data. [8] Figure 6. Determination of Z/E ratio of compound 10 by 1 H-NMR analysis. 15

16 (Z)-6-bromohex-2-en-1-ol (11) Br Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with 5-bromopent-1-ene (14.9 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 94 % consumption of 5-bromopent-1-ene. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 5:1 to 2:1) and filtered through a small plug of activated charcoal to yield 11 (16.1 mg, 90%) as a colorless oil in 97:3 Z/E ratio. 11: C 6 H 11 Br MW: H R f = 0.33 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 1H), 5.48 (dtt, J = 10.5, 7.6, 1.4 Hz, 1H), (m, 2H), 3.42 (dd, J = 8.5, 4.5 Hz, 2H), (m, 2H), (m, 2H). H not seen due to D-H exchange; 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 130.7, 130.4, 58.6, 33.3, 32.2, Analytical data for this compound was consistent with previously reported data. [9] 16

17 Figure 7. Determination of Z/E ratio of compound 11 by 1 H-NMR analysis. (Z)-3-butoxyprop-2-en-1-ol (12) 12: C 8 H 16 2 MW: Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with allyl butyl ether (11.4 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 12 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 38 % consumption of allyl butyl ether. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 5:1 to pentane:et 2 = 2:1) and filtered through a small plug of activated charcoal to yield 12 (3.9 mg, 27%) as a colorless oil in 70:30 Z/E ratio. H Rf = 0.26 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 1H), (m, 1H), (m, 2H), (m, 2H), 3.44 (t, J = 6.6 Hz, 2H), (m, 2H), (m, 2H), 0.92 (t, J = 7.4 Hz, 3H); H not seen due to D-H exchange; 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 132.2, 128.7, 70.7, 66.6, 17

18 59.0, 31.9, 19.5, Analytical data for this compound was consistent with previously reported data. [10] Figure 8. Determination of Z/E ratio of compound 12 by 1 H-NMR analysis. 18

19 (Z)-7-hydroxyhept-5-enoic acid (13) H 2 C Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with hex-5-enoic acid (11.4 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 95 % consumption of hex-5-enoic acid. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Et 2 to Et 2 :AcH = 70:1) and filtered through a small plug of activated charcoal to yield 13 (13.1 mg, 91%) as a colorless oil in 98:2 Z/E ratio. 13: C 7 H 12 3 MW: H R f = 0.33 (Et 2 :AcH = 70:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 1H), 5.65 (brs, 1H), (m, 1H), (m, 2H), 2.35 (t, J = 7.2 Hz, 2H), (m, 2H), (m, 2H). C 2 H not seen due to D-H exchange; 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 179.0, 131.8, 129.6, 58.4, 33.3, 26.6, Analytical data for this compound was consistent with previously reported data. [11] Figure 9. Determination of Z/E ratio of compound 13 by 1 H-NMR analysis. 19

20 Figure 10. Determination of Z/E ratio of compound 13 by 1 H-NMR analysis. (Z)-5-phenylpent-2-ene-1,5-diol (14) C. H H 14: C 11 H 14 2 MW: Following the general procedure, a solution of 442 L (5.0 μmol, 5.0 mol%) of Ru-6 stock solution freshly prepared was transferred to a vial charged with 1-phenylbut-3-en-1-ol (14.8 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 70 % consumption of 1-phenylbut-3-en-1-ol. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 1:1) and filtered through a small plug of activated charcoal to yield 14 (11.8 mg, 66%) as a pale yellow oil in >98:2 Z/E ratio. R f = 0.38 (Et 2 ); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 2H), (m, 1H), (m, 2H), 6.58 (d, J = 11.7 Hz, 1H), 5.88 (dt, J = 11.8, 6.4 Hz, 1H), 4.76 (dd, J = 7.8, 4.6 Hz, 1H), 4.16 (ddd, J = 12.3, 7.3, 0.9 Hz, 1H), 4.04 (dd, J = 12.4, 7.0 Hz, 1H), (m, 1H), (m, 1H). H not seen due to D-H exchange. 13 C 20

21 NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 136.6, 131.3, 131.2, 128.9, 128.4, 127.4, Analytical data for this compound was consistent with previously reported data. [12] Figure 11. Determination of Z/E ratio of compound 14 by 1 H-NMR analysis. For compound E-14 the determination of the Z/E-ratio appeared to be challenging. Hence, compound 14 was prepared as a 8:92 Z:E-mixture 14 identical reaction with Umicore M2 catalyst (8:92 Z:E-mixture: blue signals; red signals correspond to the reaction with Ru-6). Comparison of the two sets of signals allowed us to identify the doublet signal (2H; HCH 2 -) of the E-isomer for integration. 21

22 Figure 12. Identification of significant peaks for determination of E/Z-ratio of 14. (Z)-3-cyclohexylprop-2-en-1-ol (15) 15: C 9 H 16 MW: H Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with vinylcyclohexane (11.0 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene- 1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 62 % consumption of vinylcyclohexane. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 5:1) and filtered through a small plug of activated charcoal to yield 15 (7.4 mg, 53%) as a pale yellow oil in >98:2 Z/E ratio. 22

23 Figure 13. Determination of Z/E ratio of compound 15 by 1 H-NMR analysis. 23

24 R f = 0.41 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 1H), 5.39 (dd, J = 10.8, 9.5 Hz, 1H), 4.20 (dd, J = 6.7, 1.1 Hz, 2H), (m, 1H), (m, 5H), (m, 5H). 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 139.4, 126.6, 59.0, 36.7, 33.5, 26.0, Analytical data for this compound was consistent with previously reported data. [13] (Z)-3-(cyclohex-3-enyl)prop-2-en-1-ol (16) 16: C 9 H 14 MW: 138,21 H Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with 4-vinylcyclohex-1-ene (10.8 mg, 0.1 mmol, 1.0 equiv) and cis-2- butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 93 % consumption of 4-vinylcyclohex-1-ene. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane:Et 2 = 5:1) and filtered through a small plug of activated charcoal to yield 16 (6.1 mg, 44%) as a pale yellow oil in >98:2 Z/E ratio. Figure 14. Determination of Z/E ratio of compound 16 by 1 H-NMR analysis. 24

25 Figure 15. Determination of Z/E ratio of compound 16 by 1 H-NMR analysis. R f = 0.38 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): (m, 2H), (m, 1H), (m, 1H), 4.23 (dd, J = 6.7, 1.2 Hz, 2H), (m, 1H), (m, 3H), (m, 1H), (m, 1H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 138.3, 127.4, 127.0, 126.0, 58.8, 32.5, 31.8, 29.1, Analytical data for this compound was consistent with previously reported data. [3] (Z)-3-phenylprop-2-en-1-ol (17) 17: C 9 H 10 MW: H Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with styrene (10.4 mg, 0.1 mmol, 1.0 equiv) and cis-2-butene-1,4-diol (17.6 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 43 % consumption of styrene. After evaporation of the solvents the dark suspension was purified by silica gel chromatography 25

26 (Pentane:Et 2 = 5:1) and filtered through a small plug of activated charcoal to yield 17 (4.0 mg, 30%) as a pale yellow oil in 98:2 Z/E ratio. R f = 0.35 (Pentane : Et 2 = 1:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 2H), (m, 1H), (m, 2H), 6.58 (d, J = 11.7 Hz, 1H), 5.88 (dt, J = 11.8, 6.4 Hz, 1H), 4.45 (dd, J = 6.4, 1.7 Hz, 2H); H not seen due to D-H exchange; 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 136.6, 131.3, 131.2, 128.9, 128.4, 127.4, Analytical data for this compound was consistent with previously reported data. [14] Figure 16. Determination of Z/E ratio of compound 17 by 1 H-NMR analysis. (Z)-4-phenylbut-2-enyl acetate (18) 18: C 12 H 14 2 MW: Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with with allylbenzene (11.8 mg, 0.1 mmol, 1.0 equiv) and and cis-1,4-diacetoxy-2-butene (34.4 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 55 % consumption of allylbenzene. After evaporation of the solvents the 26

27 dark suspension was purified by silica gel chromatography (Pentane to Pentane:Et 2 = 20:1) and filtered through a small plug of activated charcoal to yield 18 (9.7 mg, 51%) as a pale yellow oil in 97:3 Z/E ratio. R f = 0.28 (Pentane : Et 2 = 10:1); 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 1H), (m, 1H), (m, 2H), 3.48 (d, J = 7.6 Hz, 2H), 2.08 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ), Z-isomer (major): δ 171.1, 139.9, 133.6, 128.7, 128.5, 126.3, 124.4, 60.3, 33.9, Analytical data for this compound was consistent with previously reported data. [15] Figure 17. Determination of Z/E ratio of compound 18 by 1 H-NMR analysis. (Z)-pentadec-2-enyl acetate (19) 19: C 17 H 32 2 MW: Following the general procedure, 442 L (5.0 μmol, 5.0 mol%) of freshly prepared Ru-6 stock solution was transferred to a vial charged with tetradec-1-ene (19.6 mg, 0.1 mmol, 1.0 equiv) and cis- 1,4-diacetoxy-2-butene (34.4 mg, 0.20 mmol, 2.0 equiv). The resulting solution was allowed to stir for 4 hours at 22 C. 1 H NMR 27

28 analysis with tetrachloroethane (16.8 mg, 0.1 mmol, 1.0 equiv) as internal standard revealed 64 % consumption of tetradec-1-ene. After evaporation of the solvents the dark suspension was purified by silica gel chromatography (Pentane) and filtered through a small plug of activated charcoal to yield 19 (12.3 mg, 46%) as a colorless oil in 98:2 Z/E ratio. R f = 0.47 (Pentane : Et 2 = 10:1); 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): δ (m, 1H), (m, 1H), 4.61 (d, J = 6.9 Hz, 2H), 2.09 (dd, J = 13.8, 6.9 Hz, 2H), 2.05 (s, 3H), (m, 20H), 0.87 (t, J = 6.9 Hz, 3H). 13 C NMR (101 MHz, CDCl 3 ), Z- isomer (major): δ 171.2, 135.7, 123.3, 60.6, 32.1, 29.9, 29.8 (2 C), 29.7, 29.6, 29.5, 29.4, 29.3, 27.7, 22.8, 21.2, Analytical data for this compound was consistent with previously reported data. [16] Figure 18. Determination of Z/E ratio of compound 19 by 1 H-NMR analysis 28

29 Procedure for the synthesis of Yuzu lactone; (Z)-oxacyclotridec-10-en-2-one (21). 21: C 12 H 20 2 MW: In a glovebox, a stock solution of Ru-7 (8.0 mg, 8.3 mol) in CH 2 Cl 2 (1.0 ml) was freshly prepared. A chlenk flask equipped with a J. Young valve and a PTFE screwcap was charged with ester 20 (30.0 mg, mmol, 1.0 equiv) and CH 2 Cl 2 (39 ml). Ru-7 stock solution (860 L, 7.14 mol, 6 mol%) was then added. The solution was freezepump-thaw degassed once and then heated to 40 C for 1 hour. The reaction was quenched upon addition of ethyl vinyl ether (2 ml). After evaporation of the solvents, the crude material was purified on i 2 using pentane:et 2 = 98:2 as eluent. The product was collected as colorless oil (14.0 mg, 60%). 1 H NMR (400 MHz, CDCl 3 ), Z-isomer (major): (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H). Analytical data for this compound was consistent with previously reported data. [17] Figure 19. Determination of Z/E ratio of compound 21 by 1 H-NMR analysis 29

30 General procedure for cross metathesis of methyl 9-octadecenoate experiments. M was passed through a plug of basic alumina and further heated to 185 C at 1 mbar for 2 h prior use. In a glove-box, a one dram vial was charged with (E)-methyl 9-octadecenoate (igma Aldrich, >99% purity; 544 L, 474 mg, 1.60 mmol, 1.0 equiv) and tetradecane (103.9 L, 79.4 mg, 0.40 mmol, 0.25 equiv) and the mixture was diluted with THF (952 L) to give a 1.0 M solution of (E)-methyl 9-octadecenoate. f this solution 0.25 ml (0.25 mmol) was transferred into a second one dram vial equipped with a stirring bar and 1 mol% ( mmol) of the corresponding catalyst. At the specified time points, 40 μl aliquots were taken and quenched with technical diethyl ether, and the product distribution was analyzed by GC. GC-analysis; Method Instument: himadzu GC-2014 Column Information: DB-23 (Agilent) Carrier gas: Helium Inlet temperature: 270 C Pressure: kpa Column flow: 2.77 ml / min; 40.0 cm / s plit ratio: 50 Temperature protocol: Data Analysis: Various ratios between 9-octadecene (HC) (2.5%, 5%, 10%, 15%, 20%, 25%), methyl (E)-9- octadecenoate (M) (30%, 40%, 50%, 60%, 80%, 100%), dimethyl 9-octadecenedioate (DE) (2.5%, 5%, 10%, 15%, 20%, 25%) and the internal standard (I) tetradecane (always 25%) were injected and the following GC response factors were obtained. 30

31 5 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 y = 0,0515x R² = 0,9999 y = 0,0455x R² = 0,9997 y = 0,0473x R² = 0, Product distribution in % GC-Hydrocabron / I GC-Diester / I GC-M / I Figure 20. Determination of response factors Hence, the product distribution can be determined by the following equations: % 9-octadecene (HC) = (Area of HC / Area of I) * % (E)-methyl 9-octadecenoate (M) = (Area of M / Area of I) * % dimethyl 9-octadecenedioate (DE) = (Area of DE / Area of I) * Figure 21. Note: Example to illustrate the various products with their retention time. We were unable to separate the (E/Z)-isomers of the hydrocarbon (HC). 31

32 Copies of GC-traces (Figure 5) Note: Very dilute GC-traces show small peaks of unassigned impurities which very likely are due to solvent impurities (quenching with Et 2, techn. grade). For more concentrated samples these impurities are not observed. Figure 22. elf-metathesis of methyl (E)-9-octadecenoate with Ru-1; after 9 hours. 32

33 Figure 23. elf-metathesis of methyl (E)-9-octadecenoate with Ru-1; after 24 hours. 33

34 Figure 24. elf-metathesis of methyl (E)-9-octadecenoate with Ru-4; after 24 hours. 34

35 Figure 25. elf-metathesis of methyl (E)-9-octadecenoate with Ru-6; after 24 hours. 35

36 Figure 26. elf-metathesis of methyl (E)-9-octadecenoate with Ru-7; after 24 hours. 36

37 Figure 27. elf-metathesis of methyl (E)-9-octadecenoate with Ru-8; after 24 hours. 37

38 Figure 28. elf-metathesis of methyl (E)-9-octadecenoate with Ru-9; after 24 hours. 38

39 Figure 29. elf-metathesis of methyl (E)-9-octadecenoate with Ru-10; after 24 hours. Procedure for catalyst initiation experiments (Figure 6) [17] In glovebox, a NMR tube was charged with the corresponding ruthenium complex (0.005 mmol), mesitylene (6.9 L, 0.05 mmol, 10 equiv), THF-d 8 was added (0.5 ml) and the tube was sealed with a rubber septum. The sample was equilibrated to the indicated temperature (Figure 6) in the NMR probe, then locked and shimmed. Then the sample was removed from the NMR probe, placed in a 40 C bath and ethyl vinyl ether (14.4 L, 0.15 mmol) was added. The NMR tube was placed back into the NMR probe and the reaction progress was monitored by observing the disappearance of the benzylidene signal by 1 H NMR. 39

40 Procedure for catalyst initiation experiments with trans-2-hexenyl acetate The experiment was carried out exactly as described by Grubbs and co-worker. [18] Figure 30. Determination of initiation rates for trans-2-hexenyl acetate for Ru-6 and Ru-7 40

41 X-ray structures Figure 31. RTEP of Ru-7; Cambridge tructural Database; CCDC Description of X-ray crystallographic study and structural data for Ru-7 X-ray crystallographic study: 41

42 Table 1. tructural data. Table 2. Bond lengths [Å]. Ru1 - C35 = 1.831(4) Ru1 - C1 = 2.081(4) Ru1-2 = (10) Ru1-1 = (10) Ru1-31 = 2.333(3) 1 - C51 = 1.750(4) 2 - C56 = 1.759(4) Cl1 - C52 = 1.752(4) Cl2 - C55 = 1.740(5) C1 - N2 = 1.350(5) C1 - N17 = 1.363(5) N2 - C3 = 1.448(5) N2 - C15 = 1.479(5) C3 - C8 = 1.401(6) C3 - C4 = 1.408(6) C4 - C5 = 1.388(6) C4 - C9 = 1.523(6) C5 - C6 = 1.397(7) C5 - H5 = C6 - C7 = 1.376(7) C6 - H6 = C7 - C8 = 1.399(6) C7 - H7 = C8 - C12 = 1.504(6) C9 - C11 = 1.521(6) C9 - C10 = 1.540(6) C9 - H9 = C10 - H10A = C10 - H10B = C10 - H10C = C11 - H11A = C11 - H11B = C11 - H11C = C12 - C13 = 1.533(7) C12 - C14 = 1.538(6) 42

43 C12 - H12 = C13 - H13A = C13 - H13B = C13 - H13C = C14 - H14A = C14 - H14B = C14 - H14C = C15 - C16 = 1.521(5) C15 - H15A = C15 - H15B = C16 - N17 = 1.485(5) C16 - H16A = C16 - H16B = N17 - C18 = 1.441(5) C18 - C19 = 1.402(6) C18 - C23 = 1.406(6) C19 - C20 = 1.408(6) C19 - C24 = 1.517(6) C20 - C21 = 1.363(7) C20 - H20 = C21 - C22 = 1.395(7) C21 - H21 = C22 - C23 = 1.395(6) C22 - H22 = C23 - C27 = 1.519(6) C24 - C26 = 1.536(6) C24 - C25 = 1.538(6) C24 - H24 = C25 - H25A = C25 - H25B = C25 - H25C = C26 - H26A = C26 - H26B = C26 - H26C = C27 - C28 = 1.535(6) C27 - C29 = 1.537(6) C27 - H27 = C28 - H28A = C28 - H28B = C28 - H28C = C29 - H29A = C29 - H29B = C29 - H29C = C37 = 1.385(5) 31 - C32 = 1.488(4) C32 - C34 = 1.498(6) C32 - C33 = 1.506(6) C32 - H32 = C33 - H33A = C33 - H33B = C33 - H33C = C34 - H34A = C34 - H34B = C34 - H34C = C35 - C36 = 1.456(5) C35 - H35 = C36 - C41 = 1.393(6) C36 - C37 = 1.402(5) C37 - C38 = 1.375(6) C38 - C39 = 1.407(6) C38 - H38 = C39 - C40 = 1.385(6) C39 - H39 = C40 - C41 = 1.386(6) C40 - N42 = 1.421(5) C41 - H41 = N42 - C43 = 1.348(6) N42 - H42 = 0.89(6) C43-44 = 1.203(6) C43-45 = 1.358(6) 45 - C46 = 1.440(5) C46 - C47 = 1.513(7) C46 - H46A = C46 - H46B = C47 - C48 = 1.525(7) C47 - C49 = 1.531(8) C47 - H47 = C48 - H48A = C48 - H48B = C48 - H48C = C49 - H49A = C49 - H49B = C49 - H49C = C51 - C52 = 1.402(6) C51 - C56 = 1.408(6) C52 - C53 = 1.379(6) C53 - C54 = 1.377(7) C53 - H53 = C54 - C55 = 1.389(6) 43

44 C54 - H54 = C55 - C56 = 1.391(6) C101 - Cl12 = 1.731(6) C101 - Cl11 = 1.777(6) C101 - H10D = C101 - H10E = Table 3. Angles [ ]. C35 - Ru1 - C1 = 98.01(15) C35 - Ru1-2 = 93.30(12) C1 - Ru1-2 = 84.01(10) C35 - Ru1-1 = (12) C1 - Ru1-1 = (10) 2 - Ru1-1 = 87.60(4) C35 - Ru1-31 = 79.01(13) C1 - Ru1-31 = (12) 2 - Ru1-31 = (7) 1 - Ru1-31 = 86.58(7) C Ru1 = (14) C Ru1 = (13) N2 - C1 - N17 = 107.1(3) N2 - C1 - Ru1 = 121.9(3) N17 - C1 - Ru1 = 129.1(3) C1 - N2 - C3 = 126.2(3) C1 - N2 - C15 = 113.8(3) C3 - N2 - C15 = 118.3(3) C8 - C3 - C4 = 122.5(4) C8 - C3 - N2 = 119.4(4) C4 - C3 - N2 = 118.0(4) C5 - C4 - C3 = 118.2(4) C5 - C4 - C9 = 118.7(4) C3 - C4 - C9 = 123.1(4) C4 - C5 - C6 = 120.3(4) C4 - C5 - H5 = C6 - C5 - H5 = C7 - C6 - C5 = 120.2(4) C7 - C6 - H6 = C5 - C6 - H6 = C6 - C7 - C8 = 121.9(4) C6 - C7 - H7 = C8 - C7 - H7 = C7 - C8 - C3 = 116.8(4) C7 - C8 - C12 = 121.0(4) C3 - C8 - C12 = 122.1(4) C11 - C9 - C4 = 111.9(4) C11 - C9 - C10 = 110.3(4) C4 - C9 - C10 = 111.4(4) C11 - C9 - H9 = C4 - C9 - H9 = C10 - C9 - H9 = C9 - C10 - H10A = C9 - C10 - H10B = H10A - C10 - H10B = C9 - C10 - H10C = H10A - C10 - H10C = H10B - C10 - H10C = C9 - C11 - H11A = C9 - C11 - H11B = H11A - C11 - H11B = C9 - C11 - H11C = H11A - C11 - H11C = H11B - C11 - H11C = C8 - C12 - C13 = 113.5(4) C8 - C12 - C14 = 109.1(4) C13 - C12 - C14 = 110.3(4) C8 - C12 - H12 = C13 - C12 - H12 = C14 - C12 - H12 = C12 - C13 - H13A = C12 - C13 - H13B = H13A - C13 - H13B = C12 - C13 - H13C = H13A - C13 - H13C = H13B - C13 - H13C = C12 - C14 - H14A = C12 - C14 - H14B = H14A - C14 - H14B = C12 - C14 - H14C = H14A - C14 - H14C = H14B - C14 - H14C = N2 - C15 - C16 = 102.5(3) N2 - C15 - H15A = C16 - C15 - H15A = N2 - C15 - H15B = C16 - C15 - H15B = H15A - C15 - H15B = N17 - C16 - C15 = 102.7(3) N17 - C16 - H16A =

45 C15 - C16 - H16A = N17 - C16 - H16B = C15 - C16 - H16B = H16A - C16 - H16B = C1 - N17 - C18 = 128.0(3) C1 - N17 - C16 = 112.7(3) C18 - N17 - C16 = 118.9(3) C19 - C18 - C23 = 122.2(4) C19 - C18 - N17 = 119.4(4) C23 - C18 - N17 = 118.1(3) C18 - C19 - C20 = 117.6(4) C18 - C19 - C24 = 123.9(4) C20 - C19 - C24 = 118.4(4) C21 - C20 - C19 = 121.2(4) C21 - C20 - H20 = C19 - C20 - H20 = C20 - C21 - C22 = 120.5(4) C20 - C21 - H21 = C22 - C21 - H21 = C23 - C22 - C21 = 121.0(4) C23 - C22 - H22 = C21 - C22 - H22 = C22 - C23 - C18 = 117.5(4) C22 - C23 - C27 = 119.7(4) C18 - C23 - C27 = 122.7(4) C19 - C24 - C26 = 112.6(4) C19 - C24 - C25 = 110.4(4) C26 - C24 - C25 = 109.7(4) C19 - C24 - H24 = C26 - C24 - H24 = C25 - C24 - H24 = C24 - C25 - H25A = C24 - C25 - H25B = H25A - C25 - H25B = C24 - C25 - H25C = H25A - C25 - H25C = H25B - C25 - H25C = C24 - C26 - H26A = C24 - C26 - H26B = H26A - C26 - H26B = C24 - C26 - H26C = H26A - C26 - H26C = H26B - C26 - H26C = C23 - C27 - C28 = 114.2(4) C23 - C27 - C29 = 111.0(3) C28 - C27 - C29 = 108.1(4) C23 - C27 - H27 = C28 - C27 - H27 = C29 - C27 - H27 = C27 - C28 - H28A = C27 - C28 - H28B = H28A - C28 - H28B = C27 - C28 - H28C = H28A - C28 - H28C = H28B - C28 - H28C = C27 - C29 - H29A = C27 - C29 - H29B = H29A - C29 - H29B = C27 - C29 - H29C = H29A - C29 - H29C = H29B - C29 - H29C = C C32 = 117.1(3) C Ru1 = 108.1(2) C Ru1 = 130.9(2) 31 - C32 - C34 = 111.2(3) 31 - C32 - C33 = 106.8(3) C34 - C32 - C33 = 112.8(4) 31 - C32 - H32 = C34 - C32 - H32 = C33 - C32 - H32 = C32 - C33 - H33A = C32 - C33 - H33B = H33A - C33 - H33B = C32 - C33 - H33C = H33A - C33 - H33C = H33B - C33 - H33C = C32 - C34 - H34A = C32 - C34 - H34B = H34A - C34 - H34B = C32 - C34 - H34C = H34A - C34 - H34C = H34B - C34 - H34C = C36 - C35 - Ru1 = 119.6(3) C36 - C35 - H35 = Ru1 - C35 - H35 = C41 - C36 - C37 = 119.4(4) C41 - C36 - C35 = 121.7(3) C37 - C36 - C35 = 118.8(3) C38 - C37-31 = 125.2(4) 45

46 C38 - C37 - C36 = 120.4(4) 31 - C37 - C36 = 114.4(3) C37 - C38 - C39 = 119.9(4) C37 - C38 - H38 = C39 - C38 - H38 = C40 - C39 - C38 = 119.9(4) C40 - C39 - H39 = C38 - C39 - H39 = C39 - C40 - C41 = 120.1(4) C39 - C40 - N42 = 122.7(4) C41 - C40 - N42 = 117.2(4) C40 - C41 - C36 = 120.3(4) C40 - C41 - H41 = C36 - C41 - H41 = C43 - N42 - C40 = 127.7(4) C43 - N42 - H42 = 115(4) C40 - N42 - H42 = 117(4) 44 - C43 - N42 = 126.4(5) 44 - C43-45 = 124.3(5) N42 - C43-45 = 109.3(4) C C46 = 115.1(4) 45 - C46 - C47 = 111.1(4) 45 - C46 - H46A = C47 - C46 - H46A = C46 - H46B = C47 - C46 - H46B = H46A - C46 - H46B = C46 - C47 - C48 = 110.1(4) C46 - C47 - C49 = 111.3(5) C48 - C47 - C49 = 111.3(5) C46 - C47 - H47 = C48 - C47 - H47 = C49 - C47 - H47 = C47 - C48 - H48A = C47 - C48 - H48B = H48A - C48 - H48B = C47 - C48 - H48C = H48A - C48 - H48C = H48B - C48 - H48C = C47 - C49 - H49A = C47 - C49 - H49B = H49A - C49 - H49B = C47 - C49 - H49C = H49A - C49 - H49C = H49B - C49 - H49C = C52 - C51 - C56 = 117.8(4) C52 - C51-1 = 121.7(3) C56 - C51-1 = 120.5(3) C53 - C52 - C51 = 122.8(4) C53 - C52 - Cl1 = 118.0(3) C51 - C52 - Cl1 = 119.1(3) C54 - C53 - C52 = 119.1(4) C54 - C53 - H53 = C52 - C53 - H53 = C53 - C54 - C55 = 119.1(4) C53 - C54 - H54 = C55 - C54 - H54 = C54 - C55 - C56 = 122.6(4) C54 - C55 - Cl2 = 118.1(3) C56 - C55 - Cl2 = 119.3(3) C55 - C56 - C51 = 118.4(4) C55 - C56-2 = 121.7(3) C51 - C56-2 = 119.9(3) Cl12 - C101 - Cl11 = 111.3(3) Cl12 - C101 - H10D = Cl11 - C101 - H10D = Cl12 - C101 - H10E = Cl11 - C101 - H10E = H10D - C101 - H10E =

47 Table 4. Torsion angles [ ]. N17 - C1 - N2 - C3 = (4) Ru1 - C1 - N2 - C3 = 29.3(5) N17 - C1 - N2 - C15 = -0.5(4) Ru1 - C1 - N2 - C15 = (3) C1 - N2 - C3 - C8 = -94.6(5) C15 - N2 - C3 - C8 = 101.2(5) C1 - N2 - C3 - C4 = 90.2(5) C15 - N2 - C3 - C4 = -74.1(5) C8 - C3 - C4 - C5 = -0.4(6) N2 - C3 - C4 - C5 = 174.7(4) C8 - C3 - C4 - C9 = 179.0(4) N2 - C3 - C4 - C9 = -6.0(6) C3 - C4 - C5 - C6 = 2.6(6) C9 - C4 - C5 - C6 = (4) C4 - C5 - C6 - C7 = -2.2(7) C5 - C6 - C7 - C8 = -0.4(7) C6 - C7 - C8 - C3 = 2.5(7) C6 - C7 - C8 - C12 = (4) C4 - C3 - C8 - C7 = -2.1(6) N2 - C3 - C8 - C7 = (4) C4 - C3 - C8 - C12 = 174.4(4) N2 - C3 - C8 - C12 = -0.6(6) C5 - C4 - C9 - C11 = -57.9(5) C3 - C4 - C9 - C11 = 122.7(4) C5 - C4 - C9 - C10 = 66.2(5) C3 - C4 - C9 - C10 = (4) C7 - C8 - C12 - C13 = -42.4(6) C3 - C8 - C12 - C13 = 141.2(4) C7 - C8 - C12 - C14 = 80.9(5) C3 - C8 - C12 - C14 = -95.5(5) C1 - N2 - C15 - C16 = 7.1(5) C3 - N2 - C15 - C16 = 173.3(3) N2 - C15 - C16 - N17 = -10.1(4) N2 - C1 - N17 - C18 = 165.9(4) Ru1 - C1 - N17 - C18 = -30.2(6) N2 - C1 - N17 - C16 = -6.9(4) Ru1 - C1 - N17 - C16 = 157.0(3) C15 - C16 - N17 - C1 = 11.0(4) C15 - C16 - N17 - C18 = (3) C1 - N17 - C18 - C19 = 116.9(4) C16 - N17 - C18 - C19 = -70.6(5) C1 - N17 - C18 - C23 = -68.3(5) C16 - N17 - C18 - C23 = 104.2(4) C23 - C18 - C19 - C20 = 1.2(6) N17 - C18 - C19 - C20 = 175.8(4) C23 - C18 - C19 - C24 = (4) N17 - C18 - C19 - C24 = -0.1(6) C18 - C19 - C20 - C21 = 1.2(6) C24 - C19 - C20 - C21 = 177.3(4) C19 - C20 - C21 - C22 = -2.1(7) C20 - C21 - C22 - C23 = 0.4(7) C21 - C22 - C23 - C18 = 1.9(6) C21 - C22 - C23 - C27 = (4) C19 - C18 - C23 - C22 = -2.8(6) N17 - C18 - C23 - C22 = (4) C19 - C18 - C23 - C27 = 174.4(4) N17 - C18 - C23 - C27 = -0.2(6) C18 - C19 - C24 - C26 = (4) C20 - C19 - C24 - C26 = 50.7(5) C18 - C19 - C24 - C25 = 103.6(4) C20 - C19 - C24 - C25 = -72.2(5) C22 - C23 - C27 - C28 = -22.8(5) C18 - C23 - C27 - C28 = 160.1(4) C22 - C23 - C27 - C29 = 99.7(4) C18 - C23 - C27 - C29 = -77.4(5) C C32 - C34 = -59.9(4) Ru C32 - C34 = 94.8(4) C C32 - C33 = 176.8(3) Ru C32 - C33 = -28.6(4) C1 - Ru1 - C35 - C36 = 105.1(3) 2 - Ru1 - C35 - C36 = (3) 1 - Ru1 - C35 - C36 = -81.9(3) 31 - Ru1 - C35 - C36 = 0.5(3) Ru1 - C35 - C36 - C41 = (3) Ru1 - C35 - C36 - C37 = -0.9(5) C C37 - C38 = -21.6(5) Ru C37 - C38 = 178.3(3) C C37 - C36 = 159.8(3) Ru C37 - C36 = -0.3(4) C41 - C36 - C37 - C38 = 0.7(6) C35 - C36 - C37 - C38 = (4) C41 - C36 - C37-31 = 179.4(3) C35 - C36 - C37-31 = 0.7(5) 31 - C37 - C38 - C39 = (4) C36 - C37 - C38 - C39 = 0.4(6) C37 - C38 - C39 - C40 = -0.3(7) C38 - C39 - C40 - C41 = -1.0(7) 47

48 C38 - C39 - C40 - N42 = 178.5(4) C39 - C40 - C41 - C36 = 2.2(7) N42 - C40 - C41 - C36 = (4) C37 - C36 - C41 - C40 = -2.1(6) C35 - C36 - C41 - C40 = 176.6(4) C39 - C40 - N42 - C43 = -13.4(8) C41 - C40 - N42 - C43 = 166.1(5) C40 - N42 - C43-44 = 3.0(9) C40 - N42 - C43-45 = (4) 44 - C C46 = 8.0(8) N42 - C C46 = (4) C C46 - C47 = 80.8(6) 45 - C46 - C47 - C48 = (4) 45 - C46 - C47 - C49 = 63.0(5) Ru1-1 - C51 - C52 = 172.2(3) Ru1-1 - C51 - C56 = -8.3(3) C56 - C51 - C52 - C53 = 3.3(6) 1 - C51 - C52 - C53 = (3) C56 - C51 - C52 - Cl1 = (3) 1 - C51 - C52 - Cl1 = 3.4(5) C51 - C52 - C53 - C54 = -2.0(7) Cl1 - C52 - C53 - C54 = 177.4(4) C52 - C53 - C54 - C55 = -0.9(7) C53 - C54 - C55 - C56 = 2.5(7) C53 - C54 - C55 - Cl2 = (4) C54 - C55 - C56 - C51 = -1.1(6) Cl2 - C55 - C56 - C51 = 178.4(3) C54 - C55 - C56-2 = 177.0(4) Cl2 - C55 - C56-2 = -3.6(5) C52 - C51 - C56 - C55 = -1.7(6) 1 - C51 - C56 - C55 = 178.7(3) C52 - C51 - C56-2 = (3) 1 - C51 - C56-2 = 0.6(5) Ru1-2 - C56 - C55 = (3) Ru1-2 - C56 - C51 = 7.5(3) 48

49 Figure 32. RTEP of Ru-8; Cambridge tructural Database; CCDC Description of X-ray crystallographic study and structural data for Ru-8 49

50 Table 5. tructural Data of Ru-8 Table 6. Bond lengths [Å]: Ru01 - C61 = 1.814(12) Ru01 - C3 = 2.080(14) Ru01-2 = 2.260(3) Ru01-1 = 2.296(3) Ru01-68 = 2.356(8) 1 - C52 = 1.746(13) 2 - C51 = 1.737(13) Cl1 - C53 = 1.745(15) Cl2 - C56 = 1.737(15) N1 - C3 = 1.380(15) N1 - C11 = 1.414(17) N1 - C1 = 1.480(16) N2 - C3 = 1.333(17) N2 - C31 = 1.471(14) N2 - C2 = 1.500(16) C1 - C2 = 1.538(18) C1 - H1A = C1 - H1B = C2 - H2A = C2 - H2B = C11 - C16 = 1.372(19) C11 - C12 = 1.408(18) C12 - C13 = 1.429(19) 50