Supporting Information for: Ruthenium Alkylidenes: Fast Initiators for Olefin Metathesis. Organometallics

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1 Supporting Information for: Ruthenium Alkylidenes: Fast Initiators for Olefin Metathesis Organometallics Joseph E. Williams, Mary J. Harner, and Michael B. Sponsler* Department of Chemistry Syracuse University Syracuse, NY Experimental section Kinetic plots 1 H NMR spectra 14 pages

2 Experimental Section General: All manipulations were carried out on a vacuum line or under an atmosphere of dry nitrogen in a glove-box. Solvents were dried following standard procedures. Kinetic data analyses were carried out in NMR tubes at 25 o C under N 2 atmospheres. NMR spectra were run using a 300 MHz Bruker spectrometer. Due to decomposition of 2BB, none of the compounds were obtained in analytically pure form, though 3B, 2P, and 3P were obtained without obvious impurities by NMR. C, H, and N analysis attempts for three samples of 3P all failed, each being off from the calculation for either C or H by up to 1.7%. The NMR spectra of 2BB and 2PP were all indicative of atropisomerism, with slow rotation about the Ru H 2 IMes bond. (H 2 IMes)Ru(=CHCH 3 )(Cl) 2 (3-bromopyridine) 2 (2B). Complex 2B was prepared by passing a steady stream of cis-2-butene into a solution of 1B (48 mg, mmol) in 3 ml of CH 2 Cl 2 for 2 min. The solution was put under vacuum to remove the volatiles, and the residue was then washed with pentane until the washings were pale yellow. Ethylidene 2B was obtained as a brown-red solid (38 mg, 84.3%). 1 H NMR (C 6 D 6 ): δ (q, J = 6.0 Hz, 1H, RuCH), 8.90 (bs, 2H, 3-BrPyr), 8.51 (bs, 2H, 3-BrPyr), (6H, 3-BrPyr, Mes), 6.03 (bs, 2H, 3-BrPyr), (m, 4H, NCH 2 ), 2.73 (s, 6H, Mes), 2.56 (s, 6H, Mes), 2.12 (s, 6H, Mes), 2.03 (d, J = 6.0 Hz, 3H, CHCH 3 ). 13 C{ 1 H} NMR (C 6 D 6 ): δ (bm, RuCH), (RuC), (3-BrPyr), (Mes), (Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr), (3-BrPyr), 51.4 (NCH 2 ), 20.6 (Mes), 19.3 (Mes). Some peaks were likely obscured by signals from the decomposition products. (H 2 IMes)Ru(=CHCH 2 CH 3 )(Cl) 2 (3-bromopyridine) 2 (3B). To a solution of 1B (43 mg, mmol) in 3 ml of CH 2 Cl 2 was added excess trans-3-hexene (90 µl, mmol, eq), and the solution stirred for 2 min. The solution was put under vacuum to remove the volatiles, followed by pentane washings until the washings were colorless. Propylidene 3B was obtained as a brown solid (36 mg, 89.1%). 1 H NMR (C 6 D 6 ): δ (t, J = 5.5 Hz, 1H, RuCH), 8.84 (bs, 2H, 3-BrPyr), 8.46 (bs, 2H, 3-BrPyr), (6H, 3-BrPyr, Mes), 6.05 (bs, 2H, 3-BrPyr) (m, 4H, NCH 2 ), 2.73 (s, 6H, Mes), 2.54 (s, 6H, Mes), 2.44 (dq, J = 5.5, 7.5 Hz, 2H, CHCH 2 ), 2.12 (s, 6H, Mes), 0.73 (t, J = 7.5 Hz, 3H, CH 2 CH 3 ). (In some samples, the overlapped signal at 2.12 was resolved into two equal-height signals, for example, at 2.16 and 2.12.) 13 C{ 1 H} NMR (C 6 D 6 ): δ (bm, RuCH), (RuC), (3-BrPyr), (3-BrPyr), (Mes), (Mes), (Mes), (Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3- BrPyr), (3-BrPyr), 51.6 (NCH 2 or CHCH 2 ), 51.4 (NCH 2 or CHCH 2 ), 51.2 (NCH 2 or CHCH 2 ), 21.4 (Mes), 20.7 (Mes), 19.3 (Mes), 10.3 (CH 2 CH 3 ). (H 2 IMes)Ru(=CHCH 2 CH 2 CH 3 )(Cl) 2 (3-bromopyridine) 2 (4B). To a solution of 1B (45 mg, mmol) in 3 ml of CH 2 Cl 2 was added excess trans-octene (90 µl, mmol, eq), and the solution stirred for 2 min. The solution was put under vacuum to remove the volatiles, followed by pentane washings until washings were colorless. Butylidene 4B was obtained as a brown-red solid (40 mg, 91.9%). 1 H NMR (C 6 D 6 ): δ (t, J = 5.4 Hz, RuCH), 8.80 (bs, 2H, 3-BrPyr), 8.42 (bs, 2H, 3-BrPyr), (6H, Mes), 6.10 (m, 2H, 3-BrPyr) (m, 4H, NCH 2 ), 2.73 (s, 6H, Mes), 2.53 (s, 6H, Mes), 2.43 (td, J = 7.6, 5.4 Hz, 2H, CHCH 2 ), 2.15 (s, 3H, Mes), 2.14 (s, 3H, Mes), 2.0 (m, 2H, CH 2 CH 3 ), 0.79 (t, J = 7.3 Hz, 3H, CH 2 CH 3 ). 13 C{ 1 H} NMR (C 6 D 6 ): δ (bm, RuCH), (RuC), (3-BrPyr), (3-BrPyr), (3-BrPyr), (3-BrPyr), (3-BrPyr or Mes), (Mes), (Mes), (Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-BrPyr or Mes), (3-

3 BrPyr), (3-BrPyr), 51.6 (NCH 2 or CHCH 2 ), 51.0 (NCH 2 or CHCH 2 ), 23.5 (CH 2 CH 3 ), 20.9 (Mes), 20.3 (Mes), 19.7 (Mes), 19.3 (Mes), 14.6 (CH 2 CH 3 ). Some peaks were likely obscured by signals from the decomposition products. (H 2 IMes)Ru(=CHCH 3 )(Cl) 2 (PCy 3 ) (2P). To a solution of 2B (56 mg, mmol) in 3 ml of CH 2 Cl 2 was added tricyclohexylphosphine (27 mg, mmol, 1.4 eq) in 2 ml of CH 2 Cl 2 and the solution was stirred for 2 min. The volatiles were removed under vacuum and the residue was washed with pentane until the washings were colorless. Ethylidene 2P was obtained as a brown-red solid (68% from 1B). 1 H NMR (C 6 D 6 ): δ (qd, J = 5.7, 0.7 Hz, 1H, RuCH), 6.91 (s, 2H, Mes), 6.71 (s, 2H, Mes), (m, 4H, NCH 2 ), 2.79 (s, 6H, Mes), 2.56 (s, 6H, Mes), 2.45 (m, 3H, Cy), 2.17 (s, 3H, Mes), 2.09 (s, 3H, Mes), 1.91 (d, J = 5.4 Hz, 3H, CHCH 3 ), (30H, Cy). 13 C{ 1 H} NMR (C 6 D 6 ): δ (bm, RuCH), (d, J = 75.4 Hz, RuC), (Mes), (Mes), (Mes), (Mes), (Mes), (Mes), (Mes), 52.3 (NCH 2 ), 51.5 (NCH 2 ), 47.7 (CHCH 3 ), 32.7 (d, J = 17.3 Hz, Cy), 29.9 (Cy), 28.5 (d, J = 10.2 Hz, Cy), 27.0 (Cy), 21.6 (Mes), 21.4 (Mes), 20.6 (Mes), 19.3 (Mes). 31 P{ 1 H} NMR (C 6 D 6 ): δ (H 2 IMes)Ru(=CHCH 2 CH 3 )(Cl) 2 (PCy 3 ) (3P). Same procedure as for 2P, except started with 3B. Yield: 71% from 1B. 1 H NMR (C 6 D 6 ): δ (td, J = 4.5, 1.2 Hz, 1H, RuCH), 6.90 (s, 2H, Mes), 6.74 (s, 2H, Mes), (m, 4H, NCH 2 ), 2.80 (s, 6H, Mes), 2.56 (s, 6H, Mes), 2.41 (m, 3H, Cy), 2.17 (s, 3H, Mes), 2.12 (s, 3H, Mes), 2.01 (m, 2H, CHCH 2 ), (30H, Cy), 1.08 (t, J = 7.3 Hz, 3H, CH 2 CH 3 ). 13 C{ 1 H} NMR (C 6 D 6 ): δ (bm, RuCH), (d, J = 75.6 Hz, RuC), (Mes), (Mes), (Mes), (Mes), (Mes), (Mes), (Mes), (Mes), 52.4 (NCH 2 or CHCH 2 ), 51.7 (NCH 2 or CHCH 2 ), 51.4 (NCH 2 or CHCH 2 ), 32.2 (d, J = 17.1 Hz, Cy), 29.9 (Cy), 28.5 (d, J = 9.7 Hz, Cy), 27.0 (Cy), 21.6 (Mes), 21,3 (Mes), 20.6 (Mes), 19.4 (Mes), 14.3 (CH 2 CH 3 ). 31 P{ 1 H} NMR (C 6 D 6 ): δ (H 2 IMes)Ru(=CHCH 2 CH 2 CH 3 )(Cl) 2 (PCy 3 ) (4P). Same procedure as for 2P, except started with 4B. Yield: 58% from 1B. 1 H NMR (C 6 D 6 ): δ (td, J = 4.2, 0.6 Hz, 1H, RuCH), 6.90 (s, 2H, Mes), 6.76 (s, 2H, Mes), (m, 4H, NCH 2 ), 2.79 (s, 6H, Mes), 2.55 (s, 6H, Mes), 2.44 (m, 3H, Cy), 2.17 (s, 3H, Mes), 2.13 (s, 3H, Mes), (37H, Cy, CHCH 2, CH 2 CH 3 ), 0.92 (t, J = 7.2 Hz, 3H, CH 2 CH 3 ). 13 C{ 1 H} NMR (C 6 D 6 ): δ (bm, RuCH), (d, J = 75.4 Hz, RuC), (Mes), 52.5 (NCH 2 or CHCH 2 ), 52.4 (NCH 2 or CHCH 2 ), 51.8 (NCH 2 or CHCH 2 ), (CH 2 CH 3, Cy, Mes). 31 P{ 1 H} NMR (C 6 D 6 ): δ (H 2 IMes)Ru(=CHOEt)(Cl) 2 (3-bromopyridine) 2 (5B). To a solution of 1B (9.8 mg, mmol) in 0.5 ml of C 6 D 6 in an NMR tube, was added ethyl vinyl ether (0.1 ml, 1.1 mmol, 100 eq). The formation of 5B was evident by the appearance of a new 1 H RuCH peak at δ To this sample, a solution of excess PCy 3 (20 mg, mmol, 6.5 eq) in 0.5 ml of C 6 D 6 was added and complete conversion to the peak corresponding to 5P was observed (δ 13.98).

4 Figure 1-S. Kinetic Plot for Reaction of 1P (0.01 M) with Ethyl Vinyl Ether (1.0 M) GII benzylidene 0.01 M y = x R 2 = time, s Figure 2-S. Kinetic Plot for Reaction of 1P (0.03 M) with Ethyl Vinyl Ether (1.0 M) benzylidene GII 0.03M y = -9E-05x R 2 = time, s

5 Figure 3-S. Kinetic Plot for Reaction of 2P (0.03 M) with Ethyl Vinyl Ether (1.0 M) Ethylidene GII 0.03M y = x R 2 = time, s Figure 4-S. Kinetic Plot for Reaction of 3P (0.01 M) with Ethyl Vinyl Ether (1.0 M) GII Propylidene 0.01M y = x R 2 = y = x R 2 = Time,s

6 Figure 5-S. Kinetic Plot for Reaction of 3P (0.03 M) with Ethyl Vinyl Ether (1.0 M) GII Propylidene 0.03M y = x R 2 = y = x R 2 = Time,s Figure 6-S. Kinetic Plot for Reaction of 4P (0.01 M) with Ethyl Vinyl Ether (1.0 M) Butylidene GII 0.01M y = x R 2 = time, s

7 Figure 7-S. Kinetic Plot for Reaction of 4P (0.03 M) with Ethyl Vinyl Ether (1.0 M) Butylidene GII 0.03M y = x R 2 = time,s Figure 8-S. Kinetic Plot for Reaction of 3P (0.01 M) with Ethyl Vinyl Ether (0.10 M) GII propylidene 0.01M, EVE 0.1M y = x R 2 = time,s

8 Figure 9-S. Kinetic Plot for Reaction of 3P (0.01 M) with Ethyl Vinyl Ether (2.0 M) GII Propylidene 0.01M, EVE 2.0M y = x R 2 = Time,s Figure 10-S. Plot of 1/k obs vs. [PCy 3 ]/[alkene] for Reaction of 3P (0.01 M) with Ethyl Vinyl Ether (1.0 M) PCy 3:EVE y = x R 2 = /k [PCy3]/[EVE]

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