Supporting Information for: Mechanism of N,N,N-Amide Ruthenium(II) Hydride Mediated Acceptorless Alcohol Dehydrogenation: Inner-Sphere β-h Elimination versus Outer-Sphere Bifunctional Metal Ligand Cooperativity Kuei-Nin T. Tseng, Jeff W. Kampf, and Nathaniel K. Szymczak* Department of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, MI 48109, United States Corresponding Author: nszym@umich.edu Table of Contents 1PhEtOH dehydrogenation rate dependence on [3] Complete reaction profile of 1PhEtOH dehydrogenation: standard conditions Kinetic profiles for [3] dependence studies (averaged data from three trials) Kinetic profiles for [1PhEtOH] dependence studies (averaged data from three trials) Kinetic profiles for [PPh 3] dependence studies (averaged data from three trials) Kinetic profiles for temperature dependence studies, < 7.5 M 1PhEtOH (averaged data from three trials) Kinetic profiles for temperature dependence studies, > 7.5 M 1PhEtOH (averaged data from three trials) Kinetic profiles for Hammett studies (averaged data from three trials) Kinetic profiles for isotopic labeling studies (averaged data from three trials) Kinetic profiles for 4, 4-Me, and 5 (averaged data from three trials) Kinetic profiles for 7-R (R = H, Me, Cl, OMe, OH) (averaged data from three trials) Kinetic profiles for 7-H and 7-OH with 5 equiv. NaO t Bu (averaged data from three trials) NMR spectra for Ru(HbMepi)(PPh 3)Cl[PF 6] NMR spectra for Ru(b4,6-Mepi)(PPh 3)Cl (4-Me) NMR spectra for Ru(bMepi Me )(PPh 3)OTf 2 (5) S2 S2 S2 S3 S4 S5 S6 S7 S7 S8 S9 S10 S11 S12 S13 NMR spectra for Ru(bMepi)(PPh 3)(OCH 2CF 3) (6) S14-15 NMR spectra for Ru(bpi)(PPh 3) 2Cl (7-H) NMR spectra for Ru(b4Mepi)(PPh 3) 2Cl (7-Me) NMR spectra for Ru(b4Clpi)(PPh 3) 2Cl (7-Cl) NMR spectra for Ru(b4OMepi)(PPh 3) 2Cl (7-OMe) NMR spectra for [Ru(CH 2CH 3pi)(PPh 3)] 2 (8) NMR spectra for Ru(HbMepi)(PPh 3) 2Cl 2 (9) Equilibrium Constants between 3 and Ru(bMepi)(PPh 3)(OCHPhMe) S16 S17 S18 S19 S20 S21 S22 S1
Figure S1. 1PhEtOH dehydrogenation rate dependence on [3]. Figure S4. 1PhEtOH dehydrogenation reaction profile: 35 ppm 3. Figure S2. Complete reaction profile of 1PhEtOH dehydrogenation: standard conditions. Figure S5. 1PhEtOH dehydrogenation reaction profile: standard conditions, 100 ppm 3. Figure S3. 1PhEtOH dehydrogenation reaction profile: 23 ppm 3. S2
Figure S6. 1PhEtOH dehydrogenation reaction profile: 6.5 M 1PhEtOH. Figure S9. 1PhEtOH dehydrogenation reaction profile: 8.0 M 1PhEtOH. Figure S7. 1PhEtOH dehydrogenation reaction profile: 7.0 M 1PhEtOH. Figure S8. 1PhEtOH dehydrogenation reaction profile: 7.8 M 1PhEtOH. S3
Figure S10. 1PhEtOH dehydrogenation reaction profile: 2 equiv. PPh 3. Figure S13. 1PhEtOH dehydrogenation reaction profile: 20 equiv. PPh 3. Figure S11. 1PhEtOH dehydrogenation reaction profile: 5 equiv. PPh 3. Figure S12. 1PhEtOH dehydrogenation reaction profile: 10 equiv. PPh 3. S4
Figure S14. 1PhEtOH dehydrogenation reaction profile: 90 C, [1PhEtOH] < 7.5 M. Figure S17. 1PhEtOH dehydrogenation reaction profile: 130 C, [1PhEtOH] < 7.5 M. Figure S15. 1PhEtOH dehydrogenation reaction profile: 100 C, [1PhEtOH] < 7.5 M. Figure S16. 1PhEtOH dehydrogenation reaction profile: 110 C, [1PhEtOH] < 7.5 M. S5
Figure S18. 1PhEtOH dehydrogenation reaction profile: 90 C, [1PhEtOH] > 7.5 M. Figure S21. 1PhEtOH dehydrogenation reaction profile: 120 C, [1PhEtOH] > 7.5 M. Figure S19. 1PhEtOH dehydrogenation reaction profile: 1000 C, [1PhEtOH] > 7.5 M. Figure S22. 1PhEtOH dehydrogenation reaction profile: 130 C, [1PhEtOH] > 7.5 M. Figure S20. 1PhEtOH dehydrogenation reaction profile: 110 C, [1PhEtOH] > 7.5 M. S6
Figure S23. 1-(4-methylphenyl)ethanol dehydrogenation reaction profile. Figure S26. 1PhEtOD dehydrogenation reaction profile. Figure S24. 1-(4-methoxyphenyl)ethanol dehydrogenation reaction profile. Figure S27. 1PhCH 3CDOH dehydrogenation reaction profile. Figure S28. 1PhCH 3CDOD dehydrogenation reaction profile. Figure S25. 1-(4-fluorophenyl)ethanol dehydrogenation reaction profile. S7
Figure S29. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(bMepi)(PPh 3)Cl (4). Figure S32. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(bMepi Me )(PPh 3)OTf 2 (5). Figure S30. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(b4,6-Mepi)(PPh 3)Cl (4-Me). Figure S31. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(bMepi)(PPh 3)Cl (4) and 2 equiv. NaOTf. S8
Figure S33. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(bpi)(PPh 3) 2Cl (7-H). Figure S36. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(b4OMepi)(PPh 3) 2Cl (7-OMe). Figure S34. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(b4Mepi)(PPh 3) 2Cl (7-Me). Figure S37. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(b4OHpi)(PPh 3) 2Cl (7-OH). Figure S35. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(b4Clpi)(PPh 3) 2Cl (7-Cl). S9
Figure S38. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(bpi)(PPh 3) 2Cl (7-H) with 5 equiv. NaO t Bu. Figure S39. 1PhEtOH dehydrogenation reaction profile catalyzed by Ru(b4OHpi)(PPh 3) 2Cl (7-OH) with 5 equiv. NaO t Bu. S10
Figure S40. 1 H NMR (700 MHz, CD 2Cl 2) spectrum for Ru(HbMepi)(PPh 3)Cl[PF 6]. Figure S41. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(HbMepi)(PPh 3)Cl[PF 6]. Figure S42. 31 P{ 1 H} NMR (162 MHz, CD 2Cl 2) spectrum for Ru(HbMepi)(PPh 3)Cl[PF 6]. S11
Figure S43. 1 H NMR (700 MHz, CD 2Cl 2) spectrum for Ru(b4,6-Mepi)(PPh 3)Cl (4-Me). Figure S44. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(b4,6-Mepi)(PPh 3)Cl (4-Me). Figure S45. 31 P{ 1 H} NMR (162 MHz, C 6D 6) spectrum for Ru(b4,6-Mepi)(PPh 3)Cl (4-Me). S12
Figure S46. 1 H NMR (700 MHz, CD 2Cl 2) spectrum for Ru(bMepi Me )(PPh 3)OTf 2 (5). Figure S47. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(bMepi Me )(PPh 3)OTf 2 (5). Figure S48. 31 P{ 1 H} NMR (202 MHz, CD 2Cl 2) spectrum for Ru(bMepi Me )(PPh 3)OTf 2 (5). S13
Figure S49. 1 H NMR (700 MHz, C 6D 6) spectrum for Ru(bMepi)(PPh 3)(OCH 2CF 3) (6). Figure S50. 13 C{ 1 H} NMR (176 MHz, C 6D 6) spectrum for Ru(bMepi)(PPh 3)(OCH 2CF 3) (6). Figure S51. 31 P{ 1 H} NMR (283 MHz, PhMe-d 8) spectrum for Ru(bMepi)(PPh 3)(OCH 2CF 3) (6). S14
Figure S52. 19 F NMR (376 MHz, C 6D 6) spectrum for Ru(bMepi)(PPh 3)(OCH 2CF 3) (6). S15
Figure S53. 1 H NMR (700 MHz, CD 2Cl 2) spectrum for Ru(bpi)(PPh 3) 2Cl (7-H). Figure S54. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(bpi)(PPh 3) 2Cl (7-H). Figure S55. 31 P{ 1 H} NMR (162 MHz, C 6D 6) spectrum for Ru(bpi)(PPh 3) 2Cl (7-H). S16
Figure S56. 1 H NMR (700 MHz, CD 2Cl 2) spectrum for Ru(b4Mepi)(PPh 3) 2Cl (7-Me). Figure S57. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(b4Mepi)(PPh 3) 2Cl (7-Me). Figure S58. 31 P{ 1 H} NMR (162 MHz, C 6D 6) spectrum for Ru(b4Mepi)(PPh 3) 2Cl (7-Me). S17
Figure S59. 1 H NMR (400 MHz, C 6D 6) spectrum for Ru(b4Clpi)(PPh 3) 2Cl (7-Cl). Figure S60. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(b4Clpi)(PPh 3) 2Cl (7-Cl). Figure S61. 31 P{ 1 H} NMR (162 MHz, C 6D 6) spectrum for Ru(b4Clpi)(PPh 3) 2Cl (7-Cl). S18
Figure S62. 1 H NMR (700 MHz, CD 2Cl 2) spectrum for Ru(b4OMepi)(PPh 3) 2Cl (7-OMe). Figure S63. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(b4OMepi)(PPh 3) 2Cl (7-OMe). Figure S64. 31 P{ 1 H} NMR (162 MHz, C 6D 6) spectrum for Ru(b4OMepi)(PPh 3) 2Cl (7-OMe). S19
Figure S65. 1 H NMR (700 MHz, C 6D 6) spectrum for [Ru(CH 2CH 3pi)(PPh 3)] 2 (8). Figure S66. 13 C{ 1 H} NMR (176 MHz, C 6D 6) spectrum for [Ru(CH 2CH 3pi)(PPh 3)] 2 (8). Figure S67. 31 P{ 1 H} NMR (283 MHz, C 6D 6) spectrum for [Ru(CH 2CH 3pi)(PPh 3)] 2 (8). S20
Figure S68. 1 H NMR (400 MHz, CD 2Cl 2) spectrum for Ru(HbMepi)(PPh 3) 2Cl 2 (9). Figure S69. 13 C{ 1 H} NMR (176 MHz, CD 2Cl 2) spectrum for Ru(HbMepi)(PPh 3) 2Cl 2 (9). Figure S70. 31 P{ 1 H} NMR (162 MHz, CD 2Cl 2) spectrum for Ru(HbMepi)(PPh 3) 2Cl 2 (9). S21
Table S1. Equilibrium Constants between 3 and Ru(bMepi)(PPh 3 )(OCHPhMe) Entry [1PhEtOH] (M) Ratio of 3 to alkoxide K eq 1 0.83 6.7 : 1 0.180 2 4.0 1.4 :1 0.181 3 6.0 1 : 1.11 0.183 S22