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1 Cationic Tungsten-Oxo-Alkylidene-N-Heterocyclic Carbene Complexes: Highly Active Olefin Metathesis Catalysts Roman Schowner, Wolfgang Frey, Michael R. Buchmeiser * Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, D Stuttgart, Institute of Organic Chemistry, University of Stuttgart, Pfaffenwaldring 55, D Stuttgart Supporting Information Table of contents Page General 2 Synthesis of Metal Based Compounds 3 General Procedures for Catalytic Reactions 6 Results: Activation of 3-5 with excess AlCl 3 7 NMR Study of Reaction of 5 + Excess AlCl 3 8 NMR Spectra 9 X-Ray Data 23 References 104 S1

2 General: All reactions were performed under the exclusion of air and moisture by standard Schlenk techniques unless otherwise noted. Reactions involving metal complexes were performed in an N 2 filled glove box (MBraun Labmaster 130). Glassware was either stored at 120 C over night and cooled in an evacuated antechamber or dried at 550 C under high vacuum (0.01 mbar). NMR: 1 H Spectra were recorded on a Bruker Avance III 400 (400 MHz for 1 H) spectrometer. Chemical shifts are reported in ppm from tetramethylsilane with the solvent resonance resulting from residual solvent protons (CDCl 3 : 7.26 ppm, C 6 D ppm, CD 2 Cl ppm) as reference. Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint = quintet, sept = septet, br = broad, m = multiplet), integration and coupling constants (Hz). 13 C Spectra were recorded on a Bruker Avance III 400 (100 MHz for 13 C) spectrometer. Chemical shifts are reported in ppm downfield from tetramethylsilane with the solvent resonance as reference. GC-MS: Data was obtained by using an Agilent Technologies 5975C inert MSD with triple-axis detector, an 7693 auto sampler, and a 7890A GC system equipped with a SPB-5 fused silica column (34.13 m 0.25 mm 0.25 µm film thickness). The injection temperature was set to 150 C. The column temperature ramped from 45 to 250 C within 8 min, and was then held for further 5 min. The column flow was 1.05 ml min -1. Elemental analyses were carried out at the Institute of Inorganic Chemistry, University of Stuttgart, Germany. Solvents: CH 2 Cl 2, THF, diethyl ether, toluene and pentane were dried by using an MBraun SPS-800 solvent purification system with alumina drying columns and stored over 4 Å Linde type molecular sieves (THF, toluene, DCM) or NaK alloy (Et 2 O, pentane). Deuterated solvents were filtered over activated alumina and stored over 4 Å Linde type molecular sieves inside the glove box. Substrates: All liquid substrates were dried by stirring over CaH 2 for several hours and subsequent distillation followed by filtration over activated alumina. Substrates were degassed by several freeze-pump-thaw cycles and stored over activated 4 Å molecular sieves. The following chemicals were purchased commercially: diallyldiphenylsilane, allylbenzene (ABCR), octa-1,7-diene, allylphenylsulfide, 4-octene (Alfa Aesar), diallyl ether, diethyl diallyl malonate, 1-hexene, 1-octene, hex-5-ene-1-yl acetate (Sigma-Aldrich), diallyl thioether, trimethylallylsilane (Acros Organics). N,N-Diallyl-p-toluolsulfonamide, diallyldimalonitrile, [1] 4,4-dicyanoocta-1,7- diene, [2] N-phenyl-(1-phenylbut-3-ene-1-yl)amine, [3] W(O)Cl 2 (PPhMe 2 ) 2 (CHCMe 2 Ph), [4] Ag(MeCN) 2 (BAr F ) 4, [5] Na(BAr F [6] ) 4, Li(2,6-diphenylphenolate), [7] [8] LiOCCH 3 (CF 3 ) 2 and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene [9] were prepared according to the literature. S2

3 W(O)Cl 2 (PPhMe 2 )(IMes)(CHCMe 2 Ph) (2): W(O)Cl 2 (PPhMe 2 ) 2 (CHCMe 2 Ph) (1, 2.42 g, 3.56 mmol) was dissolved in 50 ml of toluene. Separately, a solution of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (1.08 g, 3.56 mmol, 1 equiv.) in 10 ml of toluene was prepared. Both solutions were cooled at 40 C for 30 min. The cold NHC solution was added drop wise to the solution of the metal complex and the mixture was stirred for two hours at room temperature. Subsequently, the slightly turbid solution was filtered over a pad of celite and the solvent was removed in vacuo, leaving an orange oil. The oil was taken up in 50 ml of diethyl ether and filtered again. A yellow solid started to precipitate from the orange solution. The solution was put in the freezer over night at - 40 C. Yield: 2.63 g (87%) of a yellow to pale yellow solid. 1 H NMR (400 MHz, C 6 D 6 ): δ = 1.28 (d, 3H, PMe 2, J P-H = 10.1 Hz), 1.32 (s, 3H, CMe 2 Ph), 1.59 (s, 3H, CMe 2 Ph), 1.66 (d, 3H, PMe 2, J P-H = 10.3 Hz), 2.11 (s, 6H, Mes-Me), 2.24 (s, br, 6H, Mes-Me), 2.38 (s, br, 6H, Mes-Me), 6.16 (s, br, 2H, N-CH=CH-N), 6.80 (s, br, 2H, Mes-Ar), 6.83 (s, br, 2H, Mes-Ar), 6.87 (m, 3H, CMe 2 Ph), (m, 5H, Ar), 7.25 (m, 2H, Ar), 7.46 (m, 2H, PMe 2 Ph), 11.9 (d, 1H, J P-H = 3.6 Hz); 13 C NMR (100 MHz, C 6 D 6 ): δ = 14.0 (d, PMe 2, J C-P = 34.8), 15.3 (d, PMe 2, J C-P = 31.2), 19.5 (o-mes-me), 19.7 (o- Mes-Me), 21.2 (p-mes-me), 31.1 (CMe 2 Ph), 32.9 (CMe 2 Ph), 51.7 (CMe 2 Ph), (br, N-C=C-N), (p- CMe 2 Ph), (o-cme 2 Ph), (m-cme 2 Ph), (p-pph), (d, m-pph, J C-P = 2.0 Hz), (d, o-pph, J C-P = 2.7 Hz), (d, ipso-pph, J C-P = 8.6 Hz), (br), (m-mes), (o-mes), (ipso-cme 2 Ph), (d, N-C-N, J C-P = 71.1 Hz) (W=C, J C-H = Hz); 31 P NMR (160 MHz, C 6 D 6 ): δ = 8.28 (P-W), (PMe 2 Ph). Anal. calcd. for C 39 H 47 Cl 2 N 2 OPW : C, 55.40; H, 5.60; N, Found: C, 55.58; H, 5.74; N, W(O)(OTf)Cl(PPhMe 2 )(IMes)(CHCMe 2 Ph) (3): 2 (67 mg, 0,08 mmol) was dissolved in 2 ml of CH 2 Cl 2 and cooled to - 40 C. The cooled solution was added to solid silver triflate (20 mg, 1 equiv.). A colorless precipitate formed. The suspension was stirred for 30 min under the exclusion of light and then filtered over celite. After removing the solvents the residual oily product was redissolved in a minimum amount of CH 2 Cl 2 and filtered again. This step has to be repeated several times to remove residual AgCl. Yield: 61 mg (81%) of a pale yellow solid. 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 0.97 (s, 3H, CMe 2 Ph), 1.15 (d, 3H, PMe 2, J P-H = Hz), 1.36 (d, 3H, PMe 2, J P-H = Hz), 1.81 (s, 3H, CMe 2 Ph), 1.97 (s, 6H, Mes-Me), 2.16 (s, 6H, Mes-Me), 2.39 (s, 6H, Mes-Me), 6.92 (s, br, 2H, Mes-Ar), (m, 2H, Ar), 7.11 (s, br, 2H, Mes-Ar), (m, 2H, Ar), (m, 6H, Ar), 7.40 (s, 2H, N-CH=CH-N), (m, 1H, Ar), (d, 1H, W=CH, J P-H = 2.2 Hz); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = (d, PMe 2, J C-P = 35.4), 13.9 (d, PMe 2, J C-P = 31.2), 18.7 (p-mes-me), 21.5 (o-mes-me), 28.7 (CMe 2 Ph), 32.7 (CMe 2 Ph), 52.0 (CMe 2 Ph), 126.1, (br, N-C=C-N), 128.0, 128.7, 129.5, 129.5, 129.6, 129.6, (d, PPh, J C-P = 26.3 Hz), (d, PPh, J C-P = 9.3 Hz), (d, PPh, J C-P = 2.8 Hz), (p-mes), (m-mes), (o-mes), 141.4, (ipso-cme 2 Ph), (d, N-C-N, J C-P = 55.1 Hz), (d, W=C, J C-H = Hz, J C-P = 9.5 Hz); 19 F NMR (375 MHz, CD 2 Cl 2 ): δ = (OSO 2 CF 3 ); 31 P NMR (160 MHz, CD 2 Cl 2 ): δ = Anal. Calcd. for C 40 H 47 ClF 3 N 2 O 4 PSW : C, 50.09; H, 4.94; N, Found: C, 50.4; H, 5.095; N, W(O)(OCCH 3 (CF 3 ) 2 )Cl(IMes)(CHCMe 2 Ph) (4). Inside a glove box a 25 ml Schlenk flask was charged with 568 mg (0.67 mmol) of 2. The compound was dissolved in 10 ml of toluene and cooled for 30 min at - 35 C. Subsequently, 170 mg (0.75 mmol, 1 equiv.) of LiOCMe(CF 3 ) 2 were added as a solid. The suspension turned dark orange. After stirring for 3 h the reaction mixture was filtered and the solvent was evaporated. A dark orange oily solid was obtained. It was triturated with pentane (5 ml) and then dissolved in a minimum amount of diethyl ether. A yellow precipitate formed after a few hours. It was filtered off. The crude product was recrystallized from a minimum amount of diethyl ether at -35 C. The product is obtained as yellow crystals or a pale yellow solid (470 mg, 82%). 1 H NMR (400 MHz, C 6 D 6 ): δ = 1.49 (m, CMe(CF 3 ) 2, 3H), 1.54 (s, CMe 2 Ph, 3H), 1.60 (s, CMe 2 Ph, 3H), 1.91 (s, 6H, S3

4 Mes-Me), 2.05 (s, 6H, Mes-Me), 2.14 (s, 6H, Mes-Me), 5.97 (s, 2H, N-CH=CH-N), 6.39 (s, br, 2H, Mes-Ar), 6.69 (s, br, 2H, Mes-Ar), 7.00 (m, 5H, Ar), 9.76 (s, 1H, W=CH); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 17.3 (OCMe(CF 3 ) 2 ), 19.1 (o-mes-me), 19.1 (o-mes-me), 21.3 (p-mes-me), 28.8 (CMe 2 Ph), 33.4 (CMe 2 Ph), 50.3 (CMe 2 Ph), 78.4 (m, CMe(CF 3 ) 2, 3H), (N-C=C-N), (p-cme 2 Ph), (o-cme 2 Ph), (m-cme 2 Ph), 129.9, (p-mes), (m-mes), (o-mes), (ipso-mes), (CMe 2 Ph), (N-C-N), (W=C, J C-H = Hz); 19 F NMR (375 MHz, C 6 D 6 ): δ = (dq). Anal. calcd. for C 35 H 39 ClF 6 N 2 O 2 W : C, 49.28; H, 4.61; N, Found: C, 49.24; H, 4.73; N, W(O)(2,6-diphenylphenolate)Cl(IMes)(CHCMe 2 Ph) (5): 2 (850 mg, 1 mmol) was dissolved in 30 ml of toluene. Li-2,6-diphenylphenolate (266 mg, 1.06 mmol, 1.05 equiv.) was added as a solid at room temperature. The solution became turbid and was stirred for 12 h. The toluene was reduced to half the volume. The colorless precipitate was filtered off over celite. The filtrate was further reduced until precipitation started; then the solution was put in the freezer at 40 C. Overnight a yellow/orange crystalline solid formed. (830 mg, 90%). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 1.33 (s, 3H, CMe 2 Ph), 1.40 (s, 6H, Mes-Me), 1.55 (s, 3H, CMe 2 Ph), 1.80 (s. 6H, Mes-Me), 2.33 (s, 6H, Mes- Me), 6.66 (m, 2H, Ar), 6.81 (s, 2H, N-CH=CH-N), 6.83 (s, br, 2H, Mes-Ar), 6.86 (m, 1H, Ar), 6.89 (br, 2H, Mes-Ar), 6.97 (m, 4H, Ar), 7.09 (m, 1H, Ar), 7.17 (m, 2H, Ar), (m, 5H, Ar), 7.40 (m, 2H, Ar), 7.81 (m, 2H, Ar), 9.90 (s, 1H, W=CH); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 18.6 (o-mes-me), 19.2 (o-mes-me), 21.4 (p-mes-me), 29.6 (CMe 2 Ph), 32.3 (CMe 2 Ph), 50.3 (CMe 2 Ph), 120.5, 125.5, 126.4, 126.5, 127.1, 128.4, 129.2, 129.3, 129.5, 130.5, 130.8, 131, 131.8, 133.2, 134.8, 135.4, 135.4, 136.6, 139.8, 141.1, 142, (ipso-cme 2 Ph), (ipso-o-ar), (N-C-N), 288 (W=C, J C-H = Hz), (J C-H = Hz, 2 isomers). Anal. calcd. for C 49 H 49 ClN 2 O 2 W : C, 64.16; H, 5.38; N, Found: C, 64.16; H, 5.41; N, [W(O)(CHCMe 2 Ph)(IMes)(OTf)(MeCN) B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 ] (6): 6 was prepared in situ before catalytic reactions. 3 was dissolved in 5 ml of CH 2 Cl 2 and cooled at 40 C for 30 min. Ag(MeCN) 2 B(Ar F ) 4 (2.0 equiv.) was dissolved in 1 ml of CH 2 Cl 2 and this solution was added drop wise to the cold, stirred solution of 3. A colorless precipitate formed. The suspension was stirred for 30 min under the exclusion of light and then filtered through glass fiber filter. The filtrate was used as a catalyst stock solution for metathesis reactions. Alternatively the compound can be obtained as a 1:1 mixture with Ag(MeCN)(PPhMe2)B(Ar F ) 4 when the solvent is removed in vacuo. 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 1.49 (s, 3H, CMe 2 Ph), 1.92 (s, 3H, CMe 2 Ph), 2.03 (s, 6H, MeCN), 2.12 (s, 6H, Mes-Me), 2.18 (s, 6H, Mes-Me), 2.37 (s, 6H, Mes-Me), 6.96 (s, br, 2H, Mes-Ar), 7.10 (s, br, 2H, Mes-Ar), (m, 5H, Ar), 7.42 (s, 2H, N-CH=CH-N), 7.63 (s, br, 4H, BAr F ), 7.80 (s, br, 8H, BAr F ), (s, 1H, W=CH); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 2.9 (MeCN), 18.5 (o-mes-me), 19.0 (o-mes-me), 21.4 (p-mes-me), 29.2 (CMe 2 Ph), 31.0 (CMe 2 Ph), 53.5 (CMe 2 Ph), (sept, J C-F = 3.8 Hz, p-ch (BAr F )), (q, J C-F = Hz, 4x2CF 3 (BAr F )), 126.9, 127.2, 127.4, 129.2, (qq, J C-F = 31.6 Hz, J C-B = 2.7 Hz, 4xC-CF3 (BAr F )), 129.8, 130.1, 130.9, 132.4, 134.6, (s, br, 4x2C, o-ch (BAr F )), 136.9, (ipso-mes), (ipso-cme 2 Ph), (q, J C-B = 49.8 Hz, 4xBC(BAr F )), (N-C-N), (W=C, J C-H = Hz); 19 F NMR (375 MHz, CD 2 Cl 2 ): δ = (BAr F ), (OSO 2 CF 3 ). The compound cannot be separated from [Ag(MeCN)(PPhMe 2 ) + BAr F- ] Anal. calcd. for C 108 H 77 AgB 2 F 31 N 4 O 4 PSW: C, 45,67; H, 2.73; N, 1.97; Found: C, 45.0; H, 3.12; N, [W(O)(CHCMe 2 Ph)(IMes)(OCCH 3 (CF 3 ) 2 ) B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 ] (7): 4 (32 mg, mmol) was dissolved in 5 ml of CH 2 Cl 2 and cooled at 40 C for 30 min. The solution was added to solid NaB(Ar F ) 4 (33.3 mg, 1 equiv.) The suspension was stirred for 30 min. A colorless precipitate formed. Then the solution was cooled at 40 C for 30 S4

5 min and filtered through a glass fiber filter. The filtrate was reduced in vacuo to one third of the volume and filtered again. After removing the solvent an oily foam formed. It was triturated with pentane until a bright orange solid precipitated. The pentane phase was decanted and the solid was dried in vacuo. Yield 55 mg (87 %). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 1.29 (s, 3H, CMe 2 Ph), 1.32 (sept, 3H, CCH 3 (CF 3 ) 2 ), 1.64 (s, 3H, CMe 2 Ph), 1.94 (s, 6H, Mes-Me), 2.05 (s, 6H, Mes-Me), 2.37 (s, 6H, Mes-Me), 7.02 (s, br, 2H, Mes-Ar), 7.16 (s, br, 2H, Mes-Ar), (m, 5H, Ar), 7.57 (s, br, 4H, BAr F ), 7.68 (s, 2H, N-CH=CH-N), 7.74 (s, br, 8H, BAr F ), (s, 1H, W=CH); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 17.8 (o-mes-me), 17.9 (o-mes-me), 19.3 (OCMe(CF 3 ) 2 ), 21.5 (p-mes-me), 29.4 (CMe 2 Ph), 31.9 (CMe 2 Ph), 52.7 (CMe 2 Ph), 86.3 (m, OCMe(CF 3 ) 2 ), (sept, J C-F = 3.8 Hz, p-ch (BAr F )), (q, J C-F = Hz, 4x2CF 3 (BAr F )), (N-C=C-N), (o-ar), (p-ar), (m-ar), (qq, J C-F = 31.6 Hz, J C-B = 2.7 Hz, 4xC-CF3 (BAr F )), (m-mes), (m- Mes), (o- Mes), (o-mes), (p-mes), (s, br, 4x2C, o-ch (BAr F )), (ipso-mes), (ipso-cme 2 Ph), (q, J C-B = 49.8 Hz, 4xBC(BAr F )), (N-C-N), (W=C, J C-H = Hz); 19 F NMR (375 MHz, CD 2 Cl 2 ): δ = (BAr F ), (dq). Anal. Calcd. for C 67 H 51 BF 30 N 2 O 2 W : C, 47.88; H, 3.06; N, Found: C, 47.96; H, 3.279; N, [W(O)(CHCMe 2 Ph)(IMes)(MeCN)(OCCH 3 (CF 3 ) 2 ) B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 ] (7-MeCN): 4 (21,2 mg, mmol) was dissolved in 5 ml of CH 2 Cl 2 and cooled at 40 C for 30 min. The solution was added to solid Ag(MeCN) 2 B(Ar F ) 4 (26.2 mg, 1 equiv.) The suspension was stirred for 30 min under exclusion of light. A colorless precipitate formed. Then the solution was cooled at 40 C for 30 min and filtered through a glass fiber filter. The filtrate was reduced in vacuo to one third of the volume and filtered again. After removing the solvent an oily foam formed. It was triturated with pentane until a pale yellow solid precipitated. The pentane phase was decanted and the solid was dried in vacuo. Yield 39 mg (87 %). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 0.87 (s, 3H, CMe 2 Ph), 1.54 (s, br, 3H, CCH 3 (CF 3 ) 2 ), 1.76 (s, 3H, CMe 2 Ph), 1.85 (s, 3H, MeCN), 2.05 (s, 6H, Mes-Me), 2.12 (s, 6H, Mes-Me), 2.36 (s, 6H, Mes-Me), 7.05 (s, br, 2H, Mes-Ar), 7.09 (s, br, 2H, Mes-Ar), 7.17 (m, 3H, Ar), 7.28 (m, 2H, Ar), 7.37 (s, 2H, N- CH=CH-N), 7.56 (s, br, 4H, BAr F ), 7.72 (s, br, 8H, BAr F ), (s, 1H, W=CH); 19 F NMR (375 MHz, CD 2 Cl 2 ): δ = (s, br, 24F, BAr F ), (q, 3F, CF 3 ), (q, 3F, CF 3 ). Anal. Calcd. for C 69 H 54 BF 30 N 3 O 2 W : C, 48.13; H, 3.16; N, Found: C, 47.87; H, 3.483; N, [W(O)(CHCMe 2 Ph)(IMes)(2,6-diphenylphenolate) B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 ] (8): 5 (17.1 mg, mmol) was dissolved in 5 ml of CH 2 Cl 2 and cooled at 40 C for 30 min. The solution was added to solid NaB(Ar F ) 4 (16.5 mg, 1 equiv.) The suspension was stirred for 30 min. A colorless precipitate formed. Then the solution was cooled to 40 C for 30 min and filtered through a glass fiber filter. The filtrate was reduced in vacuo to one third of the volume and filtered again. After removing the solvent an oily foam formed that was triturated with pentane until a bright orange solid precipitated. The pentane phase was decanted and the solid was dried in vacuo. Yield 29 mg (89 %). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 0.62 (s, 3H, CMe 2 Ph), 1.58 (s, 3H, CMe 2 Ph), 1.68 (s, 6H, Mes-Me), 1.68 (s, 6H, Mes-Me), 2.35 (s, 6H, Mes-Me), 6.80 (s, br, 2H, Mes-Ar), 6.99 (s, br, 2H, Mes-Ar), (m, 4H), (m, 12H), (m, 4H), (m, 1H), 7.56 (s, br, p-ch (BAr F )), 7.73 (s, 8H, o-ch (BAr F )), (s, 1H, W=CH); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 18.0 (o-mes-me), 18.2 (o-mes-me), 21.5 (p-mes-me), 29.7 (CMe 2 Ph), 30.9 (CMe 2 Ph), 51.8 (CMe 2 Ph), (sept, J C-F = 3.8 Hz, p-ch (BAr F )), (q, J C-F = Hz, 4x2CF 3 (BAr F )), 125.6, 126.0, 127.6, 127.7, , 129.4, (qq, J C-F = 31.6 Hz, J C-B = 2.7 Hz, 4xC-CF3 (BAr F )), 129.9, 130.5, 130.6, 130.7, 132.0, 132.7, 133.1, (s, br, 4x2C, o-ch (BAr F )), 135.5, 136.0, (ipso-mes), (ipso-cme 2 Ph), (ipso-o-ar), (q, J C-B = 49.8 Hz, 4xBC(BAr F )), (N-C-N), (W=C, J C-H = S5

6 Hz); 19 F NMR (375 MHz, CD 2 Cl 2 ): δ = (BAr F ). Anal. Calcd. for C 81 H 61 BF 24 N 2 O 2 W : C, 55.75; H, 3.52; N, Found: C, 55.69; H, 3.913; N, [W(O)(CHCMe 2 Ph)(IMes)(MeCN) 2 (2,6-diphenylphenolate) B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 ] (8-MeCN): 5 (13.2 mg, mmol) was dissolved in 5 ml of CH 2 Cl 2 and cooled at 40 C for 30 min. The solution was added to solid Ag(MeCN) 2 B(Ar F ) 4 (15.2 mg, 1 equiv.) The suspension was stirred for 30 min. A colorless precipitate formed. Then the solution was cooled to 40 C for 30 min and filtered through a glass fiber filter. The filtrate was reduced in vacuo to one third of the volume and filtered again. After removing the solvent an oily foam formed. It was triturated with pentane until a yellow solid precipitated. The pentane phase was decanted and the solid was dried in vacuo. Yield 21 mg (84 %). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 1.35 (s, 3H, CMe 2 Ph), 1.43 (s, 3H, CMe 2 Ph), 1.58 (s, 6H, Mes-Me), 1.87 (s, 6H, MeCN), 1.88 (s, 6H, Mes-Me), 2.31 (s, 6H, Mes-Me), 6.46 (s, br, 2H, Ar), 6.95 (s, br, 2H, Mes-Ar), 6.98 (m, 2H, Ar), 7.03 (s, br, 2H, Mes-Ar), 7.06 (m, 2H, Ar), 7.15 (m, 3H, Ar), 7.24 (m, 3H, Ar), 7.35 (m, br, 3H), 7.39 (m, 3H, Ar), 7.57 (s, br, p-ch (BAr F )), 7.73 (s, 8H, o-ch (BAr F )), (s, 1H, W=CH); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 2.5 (MeCN), 18.6 (o-mes-me), 18.9 (o-mes-me), 21.4 (p-mes-me), 30.1 (CMe 2 Ph), 30.5 (CMe 2 Ph), 52.1 (CMe 2 Ph), (sept, J C-F = 3.8 Hz, p-ch (BAr F )), (MeCN), (q, J C-F = Hz, 4x2CF 3 (BAr F )), (br, N-C=C-N), 126.8, 127.2, 128.8, (qq, J C-F = 31.6 Hz, J C-B = 2.7 Hz, 4xC-CF3 (BAr F )), 129.9, 130.0, 135.4, (s, br, 4x2C, o-ch (BAr F )), 135.5, 135.6, (ipso-mes), (ipso-cme 2 Ph), (ipso-o-ar), (q, J C-B = 49.8 Hz, 4xBC(BAr F )), (N-C-N), (W=C, J C-H = Hz); 19 F NMR (375 MHz, CD 2 Cl 2 ): δ = (BAr F ). Attempted olefin metathesis reactions with complex 4: Apart from the compounds listed in Table S1, the following substrates were used: N,N-diallyltrifluoroacetamide, N,N-diallylacetamide, allyl isocyanate, N-allyl-Npropargyl p-toluenesulfonamide, allyltriphenylsilane, dimethyl allyl propargyl malonate, allylalcohol, but-3-enoic acid. Reaction conditions: room temperature, 4 h, 1,2-dichloroethane, catalyst:substrate = 1:1000. Complex 4 proved inactive in all of these reactions. Representative procedure for the in situ catalyst generation: As described in detail for compound 6, the tungsten-oxo precursor 3-5 (typically 0.05 mmol) was dissolved in 2 ml of 1,2-dichloroethane. An equimolar (2 equiv. for 6) amount of Ag(MeCN) 2 B(Ar F ) 4 or excess AlCl 3 was added to the solution. The mixture was stirred for 30 minutes and filtered over celite. The resulting solution was used as a catalyst stock solution. General procedure for ring closing metathesis and self metathesis reactions: Around 20 mg of substrate was transferred into a 10 ml dram vial. The corresponding amount of solvent was added to the substrate to obtain a 0.1 M solution. Subsequently 0.5 equiv. of dodecane (internal standard) was added. An aliquot with 1 mg of substrate was taken for the t 0 sample. A M stock solution of the catalyst was prepared. The corresponding amount stock solution (or only stock solution of 3-5, if not activated) were added to the substrate and the mixture was stirred at the indicated temperature for the indicated time period. The reactions were quenched by exposure to air and an aliquot was taken for GCMS analysis. General procedure for cross metathesis reactions with allyltrimethylsilane as cross metathesis partner: The same general procedure as for RCM and SM reactions was used. 10 equiv. of allyltrimethylsilane were added prior to the catalyst stock solution. S6

7 Representative procedure for the in situ activation of 3 5 with tris(pentafluorophenyl)borane: The tungsten-oxo precursor 3-5 (typically 0.05 mmol) was dissolved in 2 ml of 1,2-dichloroethane. An equimolar (2 equiv. for 6) amount of tris(pentafluorophenyl)borane was added to the solution. The color changed rapidly to yellow and the mixture was stirred approximately for 30 minutes. The resulting solution was used as a catalyst stock solution. Table S1 TONs obtained in olefin metathesis reactions with AlCl 3-activated 3 5 (10-fold excess with respect to W). Reactions were run at T = 25 C in 1,2-dichloroethane for 4 h using a ratio of substrate : catalyst of 5000 : 1 unless stated otherwise. Substrate/ reaction type Ring closing metathesis (RCM) 3 [a] 4 [a] 5 [a] Diallyldiphenylsilane 0 [c] 0 [c] 0 [c] N,N-diallyl-p-toluolsulfonamide 0 [c] 0 [c] 0 [c] Octa-1,7-diene 980 [c] 4300 [c] 4700 [c] Diallylmalodinitrile 0 [c] 0 [c] 0 [c] Diallyl ether 0 [c] 0 [c] 0 [c] Diallyl thioether 4800 [c] ,4-Dicyano-octa-1,7-diene 0 [c] 0 [c] 0 [c] Diethyl diallyl malonate 0 [c] 0 [c] 0 [c] Homo metathesis (HM), values in brackets = E-content Allylbenzene 640 (55) 430 (55) 410 (80) 1-Hexene 4900 (60) [c] 5000 (65) [c] 9800 (80) [e] 1-Octene 4830 (55) [c] 5000 (60) [c] 2000 (80) [c] Allyl phenyl sulfide (>95) [d] Trimethylallylsilane Cross metathesis (CM) with allyltrimethylsilane, values in brackets = E-content Hex-5-ene-1-yl acetate Octene N-phenyl-(1-phenyl-but-3-ene-1-yl)amine Self metathesis (SM), values in brackets = E-content Methyl oleate 0 [c] 0 [c] 0 [c] [a] activated with excess AlCl 3, CH 2Cl 2, room temperature, substrate : catalyst = 5000 : 1. [c] substrate : catalyst 5000 : 1, 70 C. [d] substrate : catalyst 500 : 1, 25 C. [e] substrate : catalyst : 1, 25 C. S7

8 Figure S1. Top: compound 4 in acetonitrile-d 3, middle: compound 4 + excess AlCl 3 after 30 min, bottom: compound 4 + excess AlCl 3 after 3h. S8

9 Figure S2. 1 H-NMR C 6D 6 (400 MHz) of compound 2, phosphine is partially dissociated in solution. Figure S3. 13 C-NMR C 6D 6 (100 MHz) of compound 2, phosphine is partially dissociated in solution. S9

10 Figure S4. 31 P-NMR C 6D 6 (160 MHz) of compound 2, phosphine is partially dissociated in solution. Figure S5. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 3. S10

11 Figure S6. 13 C-NMR CD 2Cl 2 (100 MHz) of compound 3. Figure S7. 19 F-NMR CD 2Cl 2 (375 MHz) of compound 3. S11

12 Figure S8. 31 P-NMR CD 2Cl 2 (160 MHz) of compound 3. Figure S9. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 4. S12

13 Figure S C-NMR CD 2Cl 2 (100 MHz) of compound 4. Figure S F-NMR CD 2Cl 2 (375 MHz) of compound 4. S13

14 Figure S12. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 5. Figure S C-NMR CD 2Cl 2 (100 MHz) of compound 5. S14

15 Figure S14. In situ 1 H-NMR CD 2Cl 2 (400 MHz) of compound 6MeCN. Figure S15. In situ 13 C-NMR CD 2Cl 2 (100 MHz) of compound 6MeCN. S15

16 Figure S16. In situ 19 F-NMR CD 2Cl 2 (375 MHz) of compound 6MeCN. Figure S17. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 7. S16

17 Figure S F-NMR CD 2Cl 2 (375 MHz) of compound 7. Figure S C-NMR CD 2Cl 2 (100 MHz) of compound 7. S17

18 Figure S20. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 8. Figure S F-NMR CD 2Cl 2 (375 MHz) of compound 8. S18

19 Figure S C-NMR CD 2Cl 2 (100 MHz) of compound 8. Figure S23. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 8-2MeCN. S19

20 Figure S F-NMR CD 2Cl 2 (375 MHz) of compound 8-2MeCN. Figure S C-NMR CD 2Cl 2 (100 MHz) of compound 8-2MeCN. S20

21 Figure S26. 1 H-NMR CD 2Cl 2 (400 MHz) of compound 7-MeCN. Figure S F-NMR CD 2Cl 2 (375 MHz) of compound 7-MeCN. S21

22 Figure S28. Single crystal x-ray structure of 2a. Selected bond lengths (pm) and angles ( ): W(1)-O(1) 169.3(2), W(1)-C(22) 188.7(3), W(1)-C(1) 220.2(3), W(1)-Cl(2) (9), W(1)-Cl(1) (8); O(1)-W(1)-C(22) (13); O(1)-W(1)-C(1) 89.58(10); C(22)-W(1)-C(1) (12); O(1)-W(1)-Cl(2) (8); C(22)-W(1)-Cl(2) (11); C(1)-W(1)-Cl(2) 80.96(8); O(1)-W(1)-Cl(1) 92.63(8); C(22)-W(1)-Cl(1) 97.02(10); C(1)- W(1)-Cl(1) (8); Cl(2)-W(1)-Cl(1) 84.67(3). S22

23 Table S2. Crystal data and structure refinement for 2. Empirical formula C43 H55 Cl2 N2 O2 P W Formula weight Temperature Wavelength 100(2) K Å Crystal system, space group triclinic, P-1 Unit cell dimensions a = (6) Å, = (3). b = (7) Å, = (3). c = (9) Å, = (3). Volume (2) Å 3 Z, Calculated density 2, Mg/m 3 Absorption coefficient mm -1 F(000) 932 Crystal size 0.38 x 0.28 x 0.16 mm Theta range for data collection 1.66 to Limiting indices -14<=h<=14, -16<=k<=16, -21<=l<=21 Reflections collected / unique / [R(int) = ] Completeness to theta = % Absorption correction numerical Max. and min. transmission and Refinement method full-matrix least-squares on F 2 Data / restraints / parameters / 222 / 579 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.a -3 S23

24 Table S3. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (A 2 x 10 3 ) for 2. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) W(1) 3266(1) 5969(1) 2282(1) 17(1) Cl(1) 2921(1) 5645(1) 3673(1) 24(1) Cl(2) 4581(1) 4616(1) 2311(1) 26(1) P(1) 1580(1) 4185(1) 1810(1) 29(1) O(1) 3340(3) 5914(3) 1252(2) 29(1) N(1) 5930(3) 7486(3) 2297(2) 19(1) C(1) 5131(4) 7124(3) 2797(2) 18(1) N(2) 5858(3) 7407(3) 3574(2) 22(1) C(2) 7105(4) 7948(4) 2750(3) 29(1) C(3) 7069(4) 7901(4) 3549(3) 30(1) C(4) 5618(4) 7609(3) 1454(2) 19(1) C(5) 5786(4) 6852(3) 764(3) 20(1) C(6) 5514(4) 7023(3) -23(3) 22(1) C(7) 5133(4) 7931(3) -125(3) 25(1) C(8) 4993(4) 8684(3) 584(3) 25(1) C(9) 5236(4) 8537(3) 1380(2) 22(1) C(10) 6267(4) 5886(4) 864(3) 26(1) C(11) 4874(5) 8104(4) -994(3) 32(1) C(12) 5145(5) 9380(4) 2156(3) 28(1) C(13) 5468(4) 7375(3) 4366(2) 23(1) C(14) 5838(4) 6664(3) 4804(3) 25(1) C(15) 5451(5) 6678(4) 5572(3) 29(1) C(16) 4740(5) 7354(4) 5901(3) 31(1) C(17) 4406(5) 8072(3) 5454(3) 29(1) C(18) 4775(5) 8085(3) 4679(3) 27(1) C(19) 6594(5) 5908(4) 4454(3) 33(1) C(20) 4321(6) 7350(4) 6734(3) 41(1) C(21) 4392(5) 8860(4) 4203(3) 30(1) S24

25 C(22) 2127(4) 6905(3) 2438(3) 21(1) C(23) 1383(4) 7469(4) 1924(3) 28(1) C(24) 0(4) 6991(4) 1900(4) 40(1) C(25) 1484(11) 7075(10) 965(7) 32(2) C(26) 1740(10) 8645(6) 2252(6) 24(2) C(27) 2069(9) 9353(7) 1771(5) 33(2) C(28) 2362(10) 10477(7) 2124(7) 47(3) C(29) 2350(13) 10878(8) 2995(7) 47(3) C(30) 1961(14) 10178(9) 3458(7) 58(3) C(31) 1686(12) 9064(8) 3104(6) 42(3) C(25A) 1768(13) 7526(11) 1105(8) 40(3) C(26A) 1615(11) 8720(7) 2522(7) 28(3) C(27A) 2195(10) 9591(8) 2249(7) 51(3) C(28A) 2422(15) 10661(9) 2749(10) 72(5) C(29A) 2081(14) 10822(9) 3544(8) 68(4) C(30A) 1418(14) 9955(10) 3793(8) 72(4) C(31A) 1192(11) 8899(8) 3286(7) 45(3) C(32) 1792(5) 3143(4) 2322(5) 54(2) C(33) 1520(5) 3543(5) 706(4) 54(2) C(34) 11(4) 4237(4) 1916(4) 32(1) C(35) -904(4) 3986(4) 1215(4) 37(1) C(36) -2100(5) 4057(5) 1314(5) 51(2) C(37) -2369(5) 4369(5) 2105(5) 59(2) C(38) -1487(5) 4610(5) 2789(5) 54(2) C(39) -274(5) 4563(4) 2710(4) 39(1) O(1X) -15(8) 8087(8) 4829(5) 53(2) C(1X) 895(19) 8748(17) 5608(12) 95(6) C(2X) 809(14) 7753(12) 6076(9) 64(4) C(3X) 631(14) 6782(12) 5391(8) 61(3) C(4X) 358(11) 7181(9) 4634(7) 42(2) O(2X) 1362(7) 726(6) -880(5) 46(2) S25

26 C(5X) 1169(10) -165(8) -1693(7) 37(2) C(6X) 1607(12) -1026(10) -1425(8) 50(3) C(7X) 1216(11) -920(8) -552(7) 41(2) C(8X) 1571(11) 208(10) -152(8) 46(3) Table S4. Bond lengths [Å] and angles [ ] for 2. W(1)-O(1) 1.704(3) W(1)-C(22) 1.949(4) W(1)-C(1) 2.246(4) W(1)-Cl(1) (10) W(1)-Cl(2) (10) W(1)-P(1) (11) P(1)-C(32) 1.800(6) P(1)-C(34) 1.811(5) P(1)-C(33) 1.813(6) N(1)-C(1) 1.375(5) N(1)-C(2) 1.378(5) N(1)-C(4) 1.453(5) C(1)-N(2) 1.367(5) N(2)-C(3) 1.388(6) N(2)-C(13) 1.439(5) C(2)-C(3) 1.344(6) C(2)-H(2) C(3)-H(3) C(4)-C(5) 1.387(6) C(4)-C(9) 1.393(6) C(5)-C(6) 1.384(5) C(5)-C(10) 1.507(6) C(6)-C(7) 1.380(6) C(6)-H(6) S26

27 C(7)-C(8) 1.394(6) C(7)-C(11) 1.512(6) C(8)-C(9) 1.381(6) C(8)-H(8) C(9)-C(12) 1.516(6) C(10)-H(10A) C(10)-H(10B) C(10)-H(10C) C(11)-H(11A) C(11)-H(11B) C(11)-H(11C) C(12)-H(12A) C(12)-H(12B) C(12)-H(12C) C(13)-C(18) 1.384(7) C(13)-C(14) 1.401(6) C(14)-C(15) 1.390(6) C(14)-C(19) 1.497(7) C(15)-C(16) 1.378(7) C(15)-H(15) C(16)-C(17) 1.403(6) C(16)-C(20) 1.510(6) C(17)-C(18) 1.397(6) C(17)-H(17) C(18)-C(21) 1.517(6) C(19)-H(19A) C(19)-H(19B) C(19)-H(19C) C(20)-H(20A) C(20)-H(20B) C(20)-H(20C) S27

28 C(21)-H(21A) C(21)-H(21B) C(21)-H(21C) C(22)-C(23) 1.535(6) C(22)-H(22) C(23)-C(26) 1.450(9) C(23)-C(25A) 1.485(14) C(23)-C(24) 1.542(7) C(23)-C(25) 1.579(12) C(23)-C(26A) 1.647(10) C(24)-H(24A) C(24)-H(24B) C(24)-H(24C) C(25)-H(25A) C(25)-H(25B) C(25)-H(25C) C(26)-C(27) 1.372(7) C(26)-C(31) 1.404(10) C(27)-C(28) 1.395(10) C(27)-H(27) C(28)-C(29) 1.420(11) C(28)-H(28) C(29)-C(30) 1.357(11) C(29)-H(29) C(30)-C(31) 1.384(11) C(30)-H(30) C(31)-H(31) C(25A)-H(25D) C(25A)-H(25E) C(25A)-H(25F) C(26A)-C(27A) 1.380(7) S28

29 C(26A)-C(31A) 1.391(11) C(27A)-C(28A) 1.399(11) C(27A)-H(27A) C(28A)-C(29A) 1.398(12) C(28A)-H(28A) C(29A)-C(30A) 1.388(12) C(29A)-H(29A) C(30A)-C(31A) 1.389(11) C(30A)-H(30A) C(31A)-H(31A) C(32)-H(32A) C(32)-H(32B) C(32)-H(32C) C(33)-H(33A) C(33)-H(33B) C(33)-H(33C) C(34)-C(39) 1.382(8) C(34)-C(35) 1.386(7) C(35)-C(36) 1.397(7) C(35)-H(35) C(36)-C(37) 1.370(10) C(36)-H(36) C(37)-C(38) 1.346(10) C(37)-H(37) C(38)-C(39) 1.401(7) C(38)-H(38) C(39)-H(39) O(1X)-C(4X) 1.320(14) O(1X)-C(1X) 1.50(2) C(1X)-C(2X) 1.65(2) C(1X)-H(1X1) S29

30 C(1X)-H(1X2) C(2X)-C(3X) 1.45(2) C(2X)-H(2X1) C(2X)-H(2X2) C(3X)-C(4X) 1.488(16) C(3X)-H(3X1) C(3X)-H(3X2) C(4X)-H(4X1) C(4X)-H(4X2) O(2X)-C(5X) 1.520(13) O(2X)-C(8X) 1.531(13) C(5X)-C(6X) 1.454(15) C(5X)-H(5X1) C(5X)-H(5X2) C(6X)-C(7X) 1.544(17) C(6X)-H(6X1) C(6X)-H(6X2) C(7X)-C(8X) 1.412(15) C(7X)-H(7X1) C(7X)-H(7X2) C(8X)-H(8X1) C(8X)-H(8X2) O(1)-W(1)-C(22) 97.77(17) O(1)-W(1)-C(1) 95.52(14) C(22)-W(1)-C(1) (15) O(1)-W(1)-Cl(1) (11) C(22)-W(1)-Cl(1) 86.52(12) C(1)-W(1)-Cl(1) 94.17(10) O(1)-W(1)-Cl(2) 92.31(12) C(22)-W(1)-Cl(2) (12) C(1)-W(1)-Cl(2) 79.97(10) S30

31 Cl(1)-W(1)-Cl(2) 82.66(4) O(1)-W(1)-P(1) 89.19(11) C(22)-W(1)-P(1) 95.09(12) C(1)-W(1)-P(1) (10) Cl(1)-W(1)-P(1) 79.39(4) Cl(2)-W(1)-P(1) 80.13(3) C(32)-P(1)-C(34) 101.9(2) C(32)-P(1)-C(33) 103.5(3) C(34)-P(1)-C(33) 105.7(3) C(32)-P(1)-W(1) (19) C(34)-P(1)-W(1) (15) C(33)-P(1)-W(1) 110.0(2) C(1)-N(1)-C(2) 111.2(3) C(1)-N(1)-C(4) 127.5(3) C(2)-N(1)-C(4) 120.2(3) N(2)-C(1)-N(1) 103.3(3) N(2)-C(1)-W(1) 131.4(3) N(1)-C(1)-W(1) 123.4(3) C(1)-N(2)-C(3) 111.5(3) C(1)-N(2)-C(13) 127.5(4) C(3)-N(2)-C(13) 120.5(3) C(3)-C(2)-N(1) 107.4(4) C(3)-C(2)-H(2) N(1)-C(2)-H(2) C(2)-C(3)-N(2) 106.5(4) C(2)-C(3)-H(3) N(2)-C(3)-H(3) C(5)-C(4)-C(9) 122.5(4) C(5)-C(4)-N(1) 119.7(4) C(9)-C(4)-N(1) 117.7(3) C(6)-C(5)-C(4) 117.6(4) S31

32 C(6)-C(5)-C(10) 120.9(4) C(4)-C(5)-C(10) 121.5(4) C(7)-C(6)-C(5) 121.8(4) C(7)-C(6)-H(6) C(5)-C(6)-H(6) C(6)-C(7)-C(8) 119.0(4) C(6)-C(7)-C(11) 120.3(4) C(8)-C(7)-C(11) 120.7(4) C(9)-C(8)-C(7) 121.1(4) C(9)-C(8)-H(8) C(7)-C(8)-H(8) C(8)-C(9)-C(4) 118.0(4) C(8)-C(9)-C(12) 121.2(4) C(4)-C(9)-C(12) 120.7(4) C(5)-C(10)-H(10A) C(5)-C(10)-H(10B) H(10A)-C(10)-H(10B) C(5)-C(10)-H(10C) H(10A)-C(10)-H(10C) H(10B)-C(10)-H(10C) C(7)-C(11)-H(11A) C(7)-C(11)-H(11B) H(11A)-C(11)-H(11B) C(7)-C(11)-H(11C) H(11A)-C(11)-H(11C) H(11B)-C(11)-H(11C) C(9)-C(12)-H(12A) C(9)-C(12)-H(12B) H(12A)-C(12)-H(12B) C(9)-C(12)-H(12C) H(12A)-C(12)-H(12C) S32

33 H(12B)-C(12)-H(12C) C(18)-C(13)-C(14) 122.7(4) C(18)-C(13)-N(2) 118.0(4) C(14)-C(13)-N(2) 119.2(4) C(15)-C(14)-C(13) 116.9(4) C(15)-C(14)-C(19) 121.5(4) C(13)-C(14)-C(19) 121.7(4) C(16)-C(15)-C(14) 122.5(4) C(16)-C(15)-H(15) C(14)-C(15)-H(15) C(15)-C(16)-C(17) 119.1(4) C(15)-C(16)-C(20) 121.7(4) C(17)-C(16)-C(20) 119.2(5) C(18)-C(17)-C(16) 120.3(5) C(18)-C(17)-H(17) C(16)-C(17)-H(17) C(13)-C(18)-C(17) 118.5(4) C(13)-C(18)-C(21) 122.1(4) C(17)-C(18)-C(21) 119.3(4) C(14)-C(19)-H(19A) C(14)-C(19)-H(19B) H(19A)-C(19)-H(19B) C(14)-C(19)-H(19C) H(19A)-C(19)-H(19C) H(19B)-C(19)-H(19C) C(16)-C(20)-H(20A) C(16)-C(20)-H(20B) H(20A)-C(20)-H(20B) C(16)-C(20)-H(20C) H(20A)-C(20)-H(20C) H(20B)-C(20)-H(20C) S33

34 C(18)-C(21)-H(21A) C(18)-C(21)-H(21B) H(21A)-C(21)-H(21B) C(18)-C(21)-H(21C) H(21A)-C(21)-H(21C) H(21B)-C(21)-H(21C) C(23)-C(22)-W(1) 139.3(3) C(23)-C(22)-H(22) W(1)-C(22)-H(22) C(26)-C(23)-C(25A) 92.4(7) C(26)-C(23)-C(22) 112.2(5) C(25A)-C(23)-C(22) 114.5(6) C(26)-C(23)-C(24) 112.2(6) C(25A)-C(23)-C(24) 116.5(6) C(22)-C(23)-C(24) 108.4(4) C(26)-C(23)-C(25) 113.3(6) C(25A)-C(23)-C(25) 21.7(6) C(22)-C(23)-C(25) 109.1(5) C(24)-C(23)-C(25) 101.1(6) C(26)-C(23)-C(26A) 16.2(5) C(25A)-C(23)-C(26A) 108.6(7) C(22)-C(23)-C(26A) 105.2(5) C(24)-C(23)-C(26A) 102.4(5) C(25)-C(23)-C(26A) 129.1(6) C(23)-C(24)-H(24A) C(23)-C(24)-H(24B) H(24A)-C(24)-H(24B) C(23)-C(24)-H(24C) H(24A)-C(24)-H(24C) H(24B)-C(24)-H(24C) C(23)-C(25)-H(25A) S34

35 C(23)-C(25)-H(25B) C(23)-C(25)-H(25C) C(27)-C(26)-C(31) 119.2(6) C(27)-C(26)-C(23) 123.8(7) C(31)-C(26)-C(23) 116.9(7) C(26)-C(27)-C(28) 120.6(6) C(26)-C(27)-H(27) C(28)-C(27)-H(27) C(27)-C(28)-C(29) 119.0(6) C(27)-C(28)-H(28) C(29)-C(28)-H(28) C(30)-C(29)-C(28) 120.2(7) C(30)-C(29)-H(29) C(28)-C(29)-H(29) C(29)-C(30)-C(31) 120.0(7) C(29)-C(30)-H(30) C(31)-C(30)-H(30) C(30)-C(31)-C(26) 120.7(7) C(30)-C(31)-H(31) C(26)-C(31)-H(31) C(23)-C(25A)-H(25D) C(23)-C(25A)-H(25E) H(25D)-C(25A)-H(25E) C(23)-C(25A)-H(25F) H(25D)-C(25A)-H(25F) H(25E)-C(25A)-H(25F) C(27A)-C(26A)-C(31A) 120.1(7) C(27A)-C(26A)-C(23) 119.8(7) C(31A)-C(26A)-C(23) 120.1(7) C(26A)-C(27A)-C(28A) 121.0(7) C(26A)-C(27A)-H(27A) S35

36 C(28A)-C(27A)-H(27A) C(29A)-C(28A)-C(27A) 118.2(7) C(29A)-C(28A)-H(28A) C(27A)-C(28A)-H(28A) C(30A)-C(29A)-C(28A) 120.6(7) C(30A)-C(29A)-H(29A) C(28A)-C(29A)-H(29A) C(29A)-C(30A)-C(31A) 120.1(7) C(29A)-C(30A)-H(30A) C(31A)-C(30A)-H(30A) C(30A)-C(31A)-C(26A) 119.6(7) C(30A)-C(31A)-H(31A) C(26A)-C(31A)-H(31A) P(1)-C(32)-H(32A) P(1)-C(32)-H(32B) H(32A)-C(32)-H(32B) P(1)-C(32)-H(32C) H(32A)-C(32)-H(32C) H(32B)-C(32)-H(32C) P(1)-C(33)-H(33A) P(1)-C(33)-H(33B) H(33A)-C(33)-H(33B) P(1)-C(33)-H(33C) H(33A)-C(33)-H(33C) H(33B)-C(33)-H(33C) C(39)-C(34)-C(35) 119.3(5) C(39)-C(34)-P(1) 119.5(4) C(35)-C(34)-P(1) 121.2(4) C(34)-C(35)-C(36) 120.1(6) C(34)-C(35)-H(35) C(36)-C(35)-H(35) S36

37 C(37)-C(36)-C(35) 119.8(6) C(37)-C(36)-H(36) C(35)-C(36)-H(36) C(38)-C(37)-C(36) 120.3(5) C(38)-C(37)-H(37) C(36)-C(37)-H(37) C(37)-C(38)-C(39) 121.1(6) C(37)-C(38)-H(38) C(39)-C(38)-H(38) C(34)-C(39)-C(38) 119.3(6) C(34)-C(39)-H(39) C(38)-C(39)-H(39) C(4X)-O(1X)-C(1X) 102.5(10) O(1X)-C(1X)-C(2X) 95.7(13) O(1X)-C(1X)-H(1X1) C(2X)-C(1X)-H(1X1) O(1X)-C(1X)-H(1X2) C(2X)-C(1X)-H(1X2) H(1X1)-C(1X)-H(1X2) C(3X)-C(2X)-C(1X) 104.2(12) C(3X)-C(2X)-H(2X1) C(1X)-C(2X)-H(2X1) C(3X)-C(2X)-H(2X2) C(1X)-C(2X)-H(2X2) H(2X1)-C(2X)-H(2X2) C(2X)-C(3X)-C(4X) 102.5(12) C(2X)-C(3X)-H(3X1) C(4X)-C(3X)-H(3X1) C(2X)-C(3X)-H(3X2) C(4X)-C(3X)-H(3X2) H(3X1)-C(3X)-H(3X2) S37

38 O(1X)-C(4X)-C(3X) 111.4(10) O(1X)-C(4X)-H(4X1) C(3X)-C(4X)-H(4X1) O(1X)-C(4X)-H(4X2) C(3X)-C(4X)-H(4X2) H(4X1)-C(4X)-H(4X2) C(5X)-O(2X)-C(8X) 107.1(8) C(6X)-C(5X)-O(2X) 103.8(9) C(6X)-C(5X)-H(5X1) O(2X)-C(5X)-H(5X1) C(6X)-C(5X)-H(5X2) O(2X)-C(5X)-H(5X2) H(5X1)-C(5X)-H(5X2) C(5X)-C(6X)-C(7X) 101.5(9) C(5X)-C(6X)-H(6X1) C(7X)-C(6X)-H(6X1) C(5X)-C(6X)-H(6X2) C(7X)-C(6X)-H(6X2) H(6X1)-C(6X)-H(6X2) C(8X)-C(7X)-C(6X) 105.1(9) C(8X)-C(7X)-H(7X1) C(6X)-C(7X)-H(7X1) C(8X)-C(7X)-H(7X2) C(6X)-C(7X)-H(7X2) H(7X1)-C(7X)-H(7X2) C(7X)-C(8X)-O(2X) 103.1(9) C(7X)-C(8X)-H(8X1) O(2X)-C(8X)-H(8X1) C(7X)-C(8X)-H(8X2) O(2X)-C(8X)-H(8X2) H(8X1)-C(8X)-H(8X2) S38

39 Table S5. Anisotropic displacement parameters (Å 2 x 10 3 ) for 2. The anisotropic displacement factor exponent takes the form: -2 2 [h 2 a* 2 U h k a* b* U 12 ]. U11 U22 U33 U23 U13 U12 W(1) 14(1) 18(1) 18(1) 3(1) 3(1) 4(1) Cl(1) 24(1) 30(1) 24(1) 14(1) 8(1) 8(1) Cl(2) 16(1) 23(1) 39(1) 5(1) 7(1) 7(1) P(1) 13(1) 20(1) 48(1) -1(1) 6(1) 5(1) O(1) 17(1) 45(2) 24(2) 9(1) 6(1) 3(1) N(1) 19(2) 21(2) 15(2) 6(1) 5(1) 0(1) C(1) 20(2) 18(2) 16(2) 6(1) 5(1) 5(2) N(2) 22(2) 24(2) 16(2) 9(1) 3(1) -3(1) C(2) 23(2) 35(2) 24(2) 10(2) 1(2) -2(2) C(3) 23(2) 34(2) 28(2) 13(2) -2(2) -3(2) C(4) 21(2) 20(2) 16(2) 7(2) 3(1) 2(2) C(5) 21(2) 22(2) 21(2) 10(2) 9(2) 3(2) C(6) 28(2) 20(2) 19(2) 6(2) 8(2) 4(2) C(7) 34(2) 21(2) 18(2) 7(2) 4(2) 1(2) C(8) 34(2) 16(2) 26(2) 8(2) 6(2) 7(2) C(9) 29(2) 17(2) 18(2) 5(2) 8(2) 4(2) C(10) 30(2) 27(2) 25(2) 10(2) 11(2) 11(2) C(11) 55(3) 24(2) 16(2) 8(2) 3(2) 6(2) C(12) 44(3) 21(2) 21(2) 7(2) 10(2) 11(2) C(13) 31(2) 24(2) 11(2) 6(2) 1(2) -2(2) C(14) 29(2) 24(2) 17(2) 4(2) -1(2) 1(2) C(15) 44(3) 22(2) 17(2) 8(2) 0(2) 1(2) C(16) 50(3) 21(2) 18(2) 7(2) 6(2) 2(2) C(17) 45(3) 18(2) 20(2) 4(2) 5(2) 3(2) C(18) 41(3) 19(2) 15(2) 3(2) 1(2) 1(2) C(19) 41(3) 31(2) 27(2) 12(2) 5(2) 7(2) C(20) 73(4) 32(3) 24(2) 13(2) 17(2) 15(3) S39

40 C(21) 50(3) 22(2) 17(2) 6(2) 6(2) 9(2) C(22) 21(2) 18(2) 23(2) 5(2) 2(2) 2(2) C(23) 24(2) 33(2) 34(2) 17(2) 4(2) 11(2) C(24) 23(2) 26(2) 74(4) 21(2) -3(2) 8(2) C(25) 38(4) 34(4) 26(4) 12(3) -4(3) 12(4) C(26) 23(4) 24(4) 27(4) 5(3) 1(3) 13(3) C(27) 37(4) 32(4) 38(4) 21(3) 8(3) 12(3) C(28) 44(4) 37(4) 66(5) 24(4) 8(4) 16(3) C(29) 46(5) 31(4) 56(5) 2(4) -4(4) 10(4) C(30) 68(5) 51(5) 57(5) 15(4) -8(4) 26(4) C(31) 48(5) 41(4) 43(5) 16(4) 3(4) 22(4) C(25A) 42(5) 44(5) 39(5) 20(4) 4(4) 14(4) C(26A) 29(4) 19(4) 37(5) 9(3) 0(4) 9(3) C(27A) 47(5) 43(5) 65(5) 17(4) 7(4) 18(4) C(28A) 70(7) 60(6) 85(7) 15(5) 6(5) 23(5) C(29A) 62(5) 59(5) 78(6) 15(4) -4(4) 16(4) C(30A) 71(6) 70(6) 74(6) 8(4) 7(4) 28(4) C(31A) 43(5) 43(4) 51(5) 5(4) 5(4) 26(4) C(32) 24(3) 22(2) 118(6) 22(3) 8(3) 7(2) C(33) 25(3) 48(3) 63(4) -27(3) 6(2) 1(2) C(34) 19(2) 21(2) 59(3) 11(2) 11(2) 7(2) C(35) 20(2) 25(2) 63(3) 11(2) 3(2) 4(2) C(36) 19(2) 37(3) 105(5) 34(3) 3(3) 9(2) C(37) 21(3) 55(4) 122(6) 45(4) 31(3) 18(2) C(38) 36(3) 49(3) 97(5) 33(3) 44(3) 20(3) C(39) 31(3) 35(3) 59(3) 18(2) 21(2) 12(2) O(1X) 44(3) 73(4) 40(3) 1(3) -5(3) 30(3) C(1X) 88(7) 94(7) 97(7) 11(5) 17(5) 26(5) C(2X) 58(5) 76(5) 59(5) 17(4) 6(4) 24(4) C(3X) 65(5) 69(5) 54(5) 25(4) 12(4) 16(4) C(4X) 43(4) 47(4) 32(4) 10(3) 12(3) 0(3) S40

41 O(2X) 43(3) 35(3) 62(4) 13(3) 17(3) 6(3) C(5X) 37(4) 34(4) 42(4) 13(3) 15(3) 5(3) C(6X) 42(4) 41(4) 66(5) 7(4) 2(4) 17(4) C(7X) 53(4) 25(4) 45(4) 25(3) -7(3) 6(3) C(8X) 40(4) 50(4) 48(4) 22(4) -3(3) 5(3) Table S6. Hydrogen coordinates (x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 2. x y z U(eq) H(2) H(3) H(6) H(8) H(10A) H(10B) H(10C) H(11A) H(11B) H(11C) H(12A) H(12B) H(12C) H(15) H(17) H(19A) H(19B) H(19C) H(20A) H(20B) H(20C) H(21A) S41

42 H(21B) H(21C) H(22) H(24A) H(24B) H(24C) H(25A) H(25B) H(25C) H(27) H(28) H(29) H(30) H(31) H(25D) H(25E) H(25F) H(27A) H(28A) H(29A) H(30A) H(31A) H(32A) H(32B) H(32C) H(33A) H(33B) H(33C) H(35) H(36) H(37) S42

43 H(38) H(39) H(1X1) H(1X2) H(2X1) H(2X2) H(3X1) H(3X2) H(4X1) H(4X2) H(5X1) H(5X2) H(6X1) H(6X2) H(7X1) H(7X2) H(8X1) H(8X2) Table S7. Torsion angles [ ] for 2. O(1)-W(1)-P(1)-C(32) 130.8(3) C(22)-W(1)-P(1)-C(32) (3) C(1)-W(1)-P(1)-C(32) 27.0(4) Cl(1)-W(1)-P(1)-C(32) -45.9(3) Cl(2)-W(1)-P(1)-C(32) 38.4(3) O(1)-W(1)-P(1)-C(34) (2) C(22)-W(1)-P(1)-C(34) -9.9(2) C(1)-W(1)-P(1)-C(34) 148.5(3) Cl(1)-W(1)-P(1)-C(34) 75.6(2) Cl(2)-W(1)-P(1)-C(34) 159.9(2) S43

44 O(1)-W(1)-P(1)-C(33) 13.8(3) C(22)-W(1)-P(1)-C(33) 111.5(3) C(1)-W(1)-P(1)-C(33) -90.1(4) Cl(1)-W(1)-P(1)-C(33) (2) Cl(2)-W(1)-P(1)-C(33) -78.7(2) C(2)-N(1)-C(1)-N(2) 1.3(5) C(4)-N(1)-C(1)-N(2) (4) C(2)-N(1)-C(1)-W(1) (3) C(4)-N(1)-C(1)-W(1) 28.0(5) O(1)-W(1)-C(1)-N(2) (4) C(22)-W(1)-C(1)-N(2) 95.4(4) Cl(1)-W(1)-C(1)-N(2) 7.9(4) Cl(2)-W(1)-C(1)-N(2) -73.8(4) P(1)-W(1)-C(1)-N(2) -62.5(5) O(1)-W(1)-C(1)-N(1) -3.8(3) C(22)-W(1)-C(1)-N(1) (3) Cl(1)-W(1)-C(1)-N(1) 169.4(3) Cl(2)-W(1)-C(1)-N(1) 87.6(3) P(1)-W(1)-C(1)-N(1) 99.0(4) N(1)-C(1)-N(2)-C(3) -1.4(5) W(1)-C(1)-N(2)-C(3) 162.8(3) N(1)-C(1)-N(2)-C(13) 169.8(4) W(1)-C(1)-N(2)-C(13) -26.1(6) C(1)-N(1)-C(2)-C(3) -0.8(5) C(4)-N(1)-C(2)-C(3) 167.8(4) N(1)-C(2)-C(3)-N(2) -0.1(5) C(1)-N(2)-C(3)-C(2) 1.0(5) C(13)-N(2)-C(3)-C(2) (4) C(1)-N(1)-C(4)-C(5) (5) C(2)-N(1)-C(4)-C(5) 89.3(5) C(1)-N(1)-C(4)-C(9) 80.0(5) S44

45 C(2)-N(1)-C(4)-C(9) -86.5(5) C(9)-C(4)-C(5)-C(6) -2.4(6) N(1)-C(4)-C(5)-C(6) (4) C(9)-C(4)-C(5)-C(10) 176.5(4) N(1)-C(4)-C(5)-C(10) 1.0(6) C(4)-C(5)-C(6)-C(7) 2.3(6) C(10)-C(5)-C(6)-C(7) (4) C(5)-C(6)-C(7)-C(8) -1.4(7) C(5)-C(6)-C(7)-C(11) 178.5(4) C(6)-C(7)-C(8)-C(9) 0.4(7) C(11)-C(7)-C(8)-C(9) (4) C(7)-C(8)-C(9)-C(4) -0.4(7) C(7)-C(8)-C(9)-C(12) 177.0(4) C(5)-C(4)-C(9)-C(8) 1.4(6) N(1)-C(4)-C(9)-C(8) 177.1(4) C(5)-C(4)-C(9)-C(12) (4) N(1)-C(4)-C(9)-C(12) -0.3(6) C(1)-N(2)-C(13)-C(18) -66.6(6) C(3)-N(2)-C(13)-C(18) 103.9(5) C(1)-N(2)-C(13)-C(14) 115.8(5) C(3)-N(2)-C(13)-C(14) -73.7(5) C(18)-C(13)-C(14)-C(15) 1.6(6) N(2)-C(13)-C(14)-C(15) 179.1(4) C(18)-C(13)-C(14)-C(19) (4) N(2)-C(13)-C(14)-C(19) -2.2(6) C(13)-C(14)-C(15)-C(16) -0.3(7) C(19)-C(14)-C(15)-C(16) (4) C(14)-C(15)-C(16)-C(17) -0.9(7) C(14)-C(15)-C(16)-C(20) 179.5(5) C(15)-C(16)-C(17)-C(18) 1.0(7) C(20)-C(16)-C(17)-C(18) (4) S45

46 C(14)-C(13)-C(18)-C(17) -1.5(7) N(2)-C(13)-C(18)-C(17) (4) C(14)-C(13)-C(18)-C(21) 179.3(4) N(2)-C(13)-C(18)-C(21) 1.7(6) C(16)-C(17)-C(18)-C(13) 0.2(7) C(16)-C(17)-C(18)-C(21) 179.4(4) O(1)-W(1)-C(22)-C(23) 2.4(5) C(1)-W(1)-C(22)-C(23) 100.0(5) Cl(1)-W(1)-C(22)-C(23) (5) Cl(2)-W(1)-C(22)-C(23) (4) P(1)-W(1)-C(22)-C(23) -87.5(5) W(1)-C(22)-C(23)-C(26) (6) W(1)-C(22)-C(23)-C(25A) -15.2(9) W(1)-C(22)-C(23)-C(24) 116.8(5) W(1)-C(22)-C(23)-C(25) 7.5(8) W(1)-C(22)-C(23)-C(26A) (5) C(25A)-C(23)-C(26)-C(27) 9.7(11) C(22)-C(23)-C(26)-C(27) 127.5(8) C(24)-C(23)-C(26)-C(27) (9) C(25)-C(23)-C(26)-C(27) 3.4(12) C(26A)-C(23)-C(26)-C(27) -165(3) C(25A)-C(23)-C(26)-C(31) (11) C(22)-C(23)-C(26)-C(31) -55.5(11) C(24)-C(23)-C(26)-C(31) 66.8(11) C(25)-C(23)-C(26)-C(31) (9) C(26A)-C(23)-C(26)-C(31) 12(2) C(31)-C(26)-C(27)-C(28) 0.9(13) C(23)-C(26)-C(27)-C(28) 177.9(10) C(26)-C(27)-C(28)-C(29) 1.8(13) C(27)-C(28)-C(29)-C(30) -5.3(18) C(28)-C(29)-C(30)-C(31) 6(2) S46

47 C(29)-C(30)-C(31)-C(26) -3(2) C(27)-C(26)-C(31)-C(30) -0.1(17) C(23)-C(26)-C(31)-C(30) (10) C(26)-C(23)-C(26A)-C(27A) 0(2) C(25A)-C(23)-C(26A)-C(27A) -5.6(12) C(22)-C(23)-C(26A)-C(27A) 117.4(9) C(24)-C(23)-C(26A)-C(27A) (9) C(25)-C(23)-C(26A)-C(27A) -13.8(14) C(26)-C(23)-C(26A)-C(31A) 177(4) C(25A)-C(23)-C(26A)-C(31A) 172.2(11) C(22)-C(23)-C(26A)-C(31A) -64.8(11) C(24)-C(23)-C(26A)-C(31A) 48.4(11) C(25)-C(23)-C(26A)-C(31A) 164.1(10) C(31A)-C(26A)-C(27A)-C(28A) 3.1(13) C(23)-C(26A)-C(27A)-C(28A) (11) C(26A)-C(27A)-C(28A)-C(29A) 2.0(16) C(27A)-C(28A)-C(29A)-C(30A) -7(2) C(28A)-C(29A)-C(30A)-C(31A) 6(2) C(29A)-C(30A)-C(31A)-C(26A) -1(2) C(27A)-C(26A)-C(31A)-C(30A) -3.6(18) C(23)-C(26A)-C(31A)-C(30A) 178.5(11) C(32)-P(1)-C(34)-C(39) 64.1(5) C(33)-P(1)-C(34)-C(39) 172.0(4) W(1)-P(1)-C(34)-C(39) -64.3(4) C(32)-P(1)-C(34)-C(35) (4) C(33)-P(1)-C(34)-C(35) -9.8(5) W(1)-P(1)-C(34)-C(35) 113.9(4) C(39)-C(34)-C(35)-C(36) -0.3(7) P(1)-C(34)-C(35)-C(36) (4) C(34)-C(35)-C(36)-C(37) -0.4(8) C(35)-C(36)-C(37)-C(38) 0.1(9) S47

48 C(36)-C(37)-C(38)-C(39) 0.9(9) C(35)-C(34)-C(39)-C(38) 1.3(7) P(1)-C(34)-C(39)-C(38) 179.6(4) C(37)-C(38)-C(39)-C(34) -1.7(8) C(4X)-O(1X)-C(1X)-C(2X) -46.6(13) O(1X)-C(1X)-C(2X)-C(3X) 34.6(15) C(1X)-C(2X)-C(3X)-C(4X) -11.5(15) C(1X)-O(1X)-C(4X)-C(3X) 45.3(14) C(2X)-C(3X)-C(4X)-O(1X) -20.3(15) C(8X)-O(2X)-C(5X)-C(6X) -15.4(11) O(2X)-C(5X)-C(6X)-C(7X) 35.1(10) C(5X)-C(6X)-C(7X)-C(8X) -45.6(12) C(6X)-C(7X)-C(8X)-O(2X) 34.8(11) C(5X)-O(2X)-C(8X)-C(7X) -12.8(11) S48

49 Table S8. Crystal data and structure refinement for 4. Empirical formula C35 H39 Cl F6 N2 O2 W Formula weight Temperature Wavelength Crystal system, space group 100(2) K Å orthorhombic, P b c a Unit cell dimensions a = (8) Å, = 90 b = (7) Å, = 90 c = (10) Å, = 90 Volume (5) A 3 Z, Calculated density 8, Mg/m 3 Absorption coefficient mm -1 F(000) 3392 Crystal size 0.19 x 0.10 x 0.10 mm Theta range for data collection 1.74 to Limiting indices -17<=h<=24, -21<=k<=21, -30<=l<=29 Reflections collected / unique / 8335 [R(int) = ] Completeness to theta = % Absorption correction numerical Max. and min. transmission and Refinement method full-matrix least-squares on F 2 Data / restraints / parameters 8335 / 0 / 437 Goodness-of-fit on F Final R indices [I>2 (I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S49

50 Table S9. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 4. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) W(1) 8310(1) 7821(1) 4091(1) 12(1) Cl(1) 7220(1) 7308(1) 4556(1) 18(1) O(1) 9014(2) 8525(2) 4035(1) 19(1) F(1) 10238(2) 6447(2) 4705(1) 32(1) N(1) 6994(2) 9010(2) 3498(2) 13(1) C(1) 7527(2) 8876(3) 3889(2) 14(1) O(2) 8805(2) 6982(2) 4610(1) 15(1) F(2) 9408(2) 5562(2) 5023(2) 41(1) N(2) 7439(2) 9520(2) 4271(2) 13(1) C(2) 6582(3) 9715(3) 3643(2) 19(1) F(3) 10115(2) 6232(2) 5602(1) 44(1) C(3) 6860(2) 10035(3) 4122(2) 16(1) F(4) 8256(2) 6222(2) 5572(1) 35(1) C(4) 6905(2) 8632(3) 2933(2) 17(1) F(5) 8195(2) 7577(2) 5662(1) 41(1) C(5) 6410(2) 7968(3) 2851(2) 18(1) F(6) 8998(2) 6862(2) 6129(1) 54(1) C(6) 6303(3) 7704(3) 2293(2) 20(1) C(7) 6630(3) 8078(3) 1834(2) 26(1) C(8) 7112(3) 8755(3) 1930(2) 23(1) C(9) 7256(3) 9045(3) 2481(2) 19(1) C(10) 5996(3) 7600(3) 3339(2) 23(1) C(11) 6483(3) 7795(4) 1228(2) 41(2) C(12) 7768(3) 9778(3) 2579(2) 27(1) C(13) 7917(2) 9707(3) 4740(2) 14(1) C(14) 7728(2) 9493(3) 5297(2) 16(1) C(15) 8221(3) 9676(3) 5728(2) 17(1) C(16) 8886(3) 10063(3) 5619(2) 18(1) S50

51 C(17) 9032(2) 10322(3) 5062(2) 16(1) C(18) 8560(2) 10156(3) 4617(2) 12(1) C(19) 6987(2) 9118(3) 5436(2) 19(1) C(20) 9420(3) 10220(3) 6093(2) 24(1) C(21) 8713(3) 10472(3) 4021(2) 19(1) C(22) 8356(2) 7247(3) 3384(2) 12(1) C(23) 8822(2) 7166(3) 2846(2) 15(1) C(24) 8300(3) 7054(3) 2337(2) 25(1) C(25) 9295(3) 7960(3) 2762(2) 24(1) C(26) 9333(2) 6400(3) 2922(2) 15(1) C(27) 9403(3) 5772(3) 2507(2) 25(1) C(28) 9882(3) 5093(3) 2576(2) 29(1) C(29) 10280(3) 5020(3) 3065(2) 23(1) C(30) 10230(2) 5636(3) 3480(2) 19(1) C(31) 9756(2) 6310(3) 3410(2) 15(1) C(32) 9180(3) 7049(3) 5122(2) 18(1) C(33) 9605(3) 7863(3) 5210(2) 38(2) C(34) 9740(3) 6318(3) 5108(2) 29(1) C(35) 8661(3) 6909(4) 5622(3) 34(2) Table S10. Bond lengths [Å] and angles [ ] for 4. W(1)-O(1) 1.704(3) W(1)-C(22) 1.885(4) W(1)-O(2) 2.010(3) W(1)-C(1) 2.246(4) W(1)-Cl(1) (11) F(1)-C(34) 1.327(6) N(1)-C(1) 1.353(6) N(1)-C(2) 1.385(5) N(1)-C(4) 1.457(6) S51