Chapter 5: Catalytic N-N Coupling of Aryl Azides to Yield Azoarenes with a Ru(I)
5.5. Experimental Section
5.5.4 Synthetic Details
Synthesis of {[SiPiPr3]Ru(NAr)}OTf (Ar = p--C6H4CF3) (5.7-CF3). [SiPiPr3]Ru(N2) (100 mg, 0.14 mmol) was dissolved in 10 mL of Et2O and cooled to −78 oC. p- CF3C6H4N3 (26 mg, 0.14 mmol) was diluted with 2 mL Et2O and also cooled to −78 oC.
The azide solution was added dropwise to the solution of [SiPiPr3]Ru(N2), resulting in an immediate color change from green to red/purple. The solution was stirred for 10 min at
−78 oC and for 10 min at room temperature. The solution was cooled to −78 oC again, and AgOTf (36 mg, 0.14 mmol) was added in one portion. The solution gradually precipitated a green solid, along with black Ag metal. The mixture was filtered through celite, and the green product was extracted into THF. The dark green solution was concentrated, and the product was recrystallized from layering pentane over a concentrated THF solution of green 5.7-CF3 to yield crystals suitable for X-ray diffraction (82 mg, 59%). 1H NMR (d8-THF, δ): 8.31 (d, J = 8.0 Hz, 2H), 8.11 (d, J = 7.5 Hz, 3H), 7.77 (m, 3H), 7.59 (d, J = 8.5 Hz, 2H), 7.52 (t, J = 8.0 Hz, 3H), 7.41 (t, J = 7.5
Hz, 3H), 2.76 (br, 6H), 1.11 (dd, J = 14.5, 6.5 Hz, 18H), 0.52 (m, 18H). 13C{1H} NMR (d8-THF, δ): 156.1, 141.2, 133.7, 132.0, 130.4, 129.2, 128.3, 120.8, 32.4, 19.5, 19.2.
19F{1H} NMR (d8-THF, δ): −62.3, −77.3. 31P{1H} NMR (d8-THF, δ): 109.8. Anal. Calcd for C44H58NO3F6SiP3SRu: C, 51.96; H, 5.75; N. 1.38. Found: C, 51.59; H, 5.76; N, 1.25.
Synthesis of {[SiPiPr3]Ru(N3Ar)}BArF4 (5.8-OMe, Ar = C6H4OMe).
{[SiPiPr3]Ru(N2)}BArF4 (46 mg, 0.029 mmol) was dissolved in 4 mL Et2O and cooled to
−78 oC. p-MeOC6H4N3 (4.4 mg, 0.029 mmol) was dissolved in 1 mL Et2O and also cooled to −78 oC. The azide solution was added dropwise to the {[SiPiPr3]Ru(N2)}BArF4
solution, which resulted in an immediate color change from orange to red. The solution was stirred at room temperature for 10 min and concentrated to yield red 5.8-OMe (44 mg, 89%). Crystals suitable for X-ray diffraction were grown from layering pentane over a concentrated ether solution of 5.8-OMe at −35 oC. 1H NMR (d8-THF, δ): 8.34 (d, J = 7.2 Hz, 3H), 7.79 (s, 8H), 7.64 (br, 3H), 7.57 (s, 4H), 7.47 (t, J = 7.2 Hz, 3H), 7.38 (t, J = 7.5 Hz, 3H), 7.16 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 9.0 Hz, 2H), 3.78 (s, 3H), 2.10 (br, 6H), 1.17 (br, 18H), 0.83 (br, 18H). 13C{1H} NMR (d8-THF, δ): 163.8 (m), 160.4, 154.4, 144.0, 136.5, 134.9,131.6, 131.0, 130.8, 130.0, 129.6, 127.4, 123.1, 123.0, 119.1, 117.1, 67.2, 56.5, 20.8 (br), 16.5. 19F{1H} NMR (d8-THF, δ): −61.2. 31P{1H} NMR (d8-THF, δ): 72.9.
Synthesis of {[SiPiPr3]Ru(NAr)}BArF4 (5.7-OMe). {[SiPiPr3]Ru(N3Ar)}BArF4 (8-OMe, Ar = C6H4OMe) (40 mg, 0.023 mmol) was dissolved in 2 mL THF and charged in a 4 mL quartz cuvette. Excess p-MeOC6H4N3 (4 mg, 0.027 mmol) was added to the cuvette and the red solution was photolyzed. The progress of the conversion was monitored by
31P{1H} NMR spectroscopy. After the conversion was complete (approximately 1 h), the green solution was concentrated, and the oily material was triturated with pentane (5 x 3
mL) to yield the green 5.7-OMe (32 mg, 83%). Crystals suitable for X-ray diffraction were grown by layering pentane over a concentrated ether solution of 5.7-OMe at −35 oC.
1H NMR (d8-THF, δ): 8.14 (d, J = 7.5 Hz, 3H), 7.78 (s, 8H), 7.77 (m, 3H), 7.57 (s, 4H), 7.44-6.85 (m, 10H), 3.83 (s, 3H), 2.74 (br, 6H), 1.12 (m, 18H), 0.55 (m, 18H). 13C{1H}
NMR (d8-THF, δ): 163.6 (m), 162.1, 157.2 (m), 142.6 (m), 136.5, 134.9, 133.0, 131.0, 130.8, 130.5, 130.2, 129.6, 127.5, 125.3, 125.2, 123.1, 119.1, 117.6, 57.1, 33.3, 20.5, 20.3. ). 19F{1H} NMR (d8-THF, δ): −61.4. 31P{1H} NMR (d8-THF, δ): 106.4.
Synthesis of {[SiPiPr3]Ru(N2)}PF6 (5.9-PF6), {[SiPiPr3]Ru(N3Ar)}PF6 (5.8-OMe), and {[SiPiPr3]Ru(NAr)}PF6 (Ar = C6H4OMe) (5.7-OMe). 5.9-PF6: [SiPiPr3]Ru(N2) (35 mg, 0.048 mmol) was dissolved in 5 mL THF. AgPF6 (12 mg, 0.048 mmol) was dissolved in 1 mL THF and both solution were cooled to −78 oC. The AgPF6 solution was added dropwise to the solution of [SiPiPr3]Ru(N2), causing an immediate darkening of the solution. The solution was stirred for 10 min, filtered through celite, and concentrated.
The solid was washed with Et2O and dried to yield 5.9-PF6 (31 mg, 74%). 1H NMR (d8- THF, δ): 8.25 (d, J = 6.9 Hz, 3H), 7.64 (d, J = 7.2 Hz, 3H), 7.42 (t, J = 6.9 Hz, 3H), 7.33 (t, J = 6.6 Hz, 3H), 2.44 (br, 6H), 1.22 (s, 18H), 0.86 (s, 18H). %). 13C {1H} NMR (d8- THF, δ): 155.2, 144.7, 134.2, 131.8, 131.0, 129.4, 29.3, 21.3, 20.5. 19F{1H} NMR (d8- THF, δ): −72.9 (d, J = 715 Hz). 31P{1H} NMR (d8-THF, δ): 67.5, −142.1 (sep, J = 715 Hz). 5.8-OMe, PF6− anion: {[SiPiPr3]Ru(N2)}PF6 (17 mg, 0.020 mmol) was dissolved in 6 mL THF and cooled to −78 oC. p-MeOC6H4N3 (2.9 mg, 0.020 mmol) was added to the solution in one portion, resulting in an immediate color change to red. The solution was stirred for 10 min, and concentrated to yield red 5.8-OMe (18 mg, 94%). 1H NMR (d8- THF, δ): 8.26 (d, J = 7.0 Hz, 3H), 7.61 (br, 3H), 7.41 (t, J = 8.0 Hz, 3H), 7.32 (t, J = 8.0
Hz, 3H), 7.07 (d, J = 9.0 Hz, 2H), 6.97 (t, J = 9.0 Hz, 3H), 3.74 (s, 3H), 2.15 (br, 6H), 1.13 (s, 18H), 0.78 (s, 18H). 13C{1H} NMR (d8-THF, δ): 159.8, 155.1, 144.5, 134.6, 132.8, 131.7, 131.3, 129.6, 122.6, 117.2, 56.6, 30.4, 21.2, 20.7. 19F{1H} NMR (d8-THF, δ): −71.7 (d, J = 711 Hz). 31P{1H} NMR (d8-THF, δ): 72.6, −142.9 (sep, J = 711 Hz).
5.7-OMe, PF6−
anion: The synthesis of 5.7-OMe was performed in a three-step sequence, without isolation of intermediate products, 5.9-PF6 and 5.8-OMe.
[SiPiPr3]Ru(N2) (50 mg, 0.068 mmol) was dissolved in 8 mL THF. AgPF6 (17 mg, 0.068 mmol) was dissolved in 2 mL THF. Both were cooled to −78 oC and the AgPF6 solution was added dropwise to the solution of [SiPiPr3]Ru(N2), leading to an immediate color change from green to dark brown. The mixture was stirred at −78 oC for 5 min, and stirred at room temperature for 10 min The mixture was filtered through celite, and the filtrate was cooled to −78 oC. A THF solution of p-MeOC6H4N3 (20 mg, 0.14 mmol) was added dropwise to the filtrate, resulting in a color change to red. The red solution of 5.8- OMe was stirred for 10 min, and charged into a 100 mL quartz flask. The solution was photolyzed, and the progress of the reaction was monitored by 31P{1H} NMR spectroscopy. After the conversion was complete (approximately 1h), the solution was concentrated, and the residues were washed with Et2O to yield green 5.7-OMe (57 mg, 86% overall). Recrystallization by layering pentane over a THF solution of 5.7-OMe yielded crystals suitable for X-ray diffraction. 1H NMR (d8-THF, δ): 8.18 (d, J = 8.4 Hz, 2H), 8.12 (d, J = 7.2 Hz, 3H), 7.77 (m, 3H), 7.52 (t, J = 7.2 Hz, 3H), 7.41 (t, J = 6.9 Hz, 3H), 6.93 (d, J = 9.0 Hz, 2H), 3.85 (s, 3H), 2.76 (m, 6H), 1.11 (m, 18H), 0.55 (m, 18H).
13C NMR (d8-THF, δ): 162.3 (m), 157.3(m), 142.7 (m), 134.8 (m), 132.8, 131.2, 130.1, 125.5, 117.9, 57.3, 33.4 (m), 20.6, 20.3. 31P NMR (d8-THF, δ): 106.5, −143.6 (sep, J =
738 Hz). Anal. Calcd for C43H61NOF6SiP4Ru: C, 52.97; H, 6.31; N. 1.44. Found: C, 52.23; H, 6.18; N, 1.32.
Synthesis of [SiPiPr2P(=NAr)Ru]PF6 (5.10). [SiPiPr3]Ru(N2) (17 mg, 0.023 mmol) was dissolved in 5 mL THF. AgPF6 (5.8 mg, 0.023 mmol) was dissolved in 1 mL THF. Both solutions were cooled to −78 oC and the AgPF6 solution was added dropwise to the [SiPiPr3]Ru(N2) solution, resulting in an immediate darkening of the solution. The mixture was stirred for 2 min at low temperature and then stirred for 2 min at room temperature.
The mixture was filtered through celite, and the filtrate was cooled to −78 oC again. p- MeOC6H4N3 (6.9 mg, 0.046 mmol) in 1 mL THF was added to the solution dropwise, leading to a color change to red. The solution was stirred for 5 min and charged into a 100 mL quartz flask. The solution was photolyzed for two days. The solution was concentrated and washed with Et2O to yield 5.10 (14 mg, 62%). Crystals suitable for X- ray diffraction were obtained by vapor diffusion of pentane into a concentrated solution of 5.10. 1H NMR (d8-THF, δ): 7.92-7.83 (m, 2H), 7.66 (dd, J = 7.5, 4.2 Hz, 2H), 7.49 (d, J = 7.2 Hz, 2H), 7.43-7.23 (m, 6H), 6.66 (d, J = 6.0 Hz, 1H), 5.47 (d, J = 6.0 Hz, 1H), 5.31 (t, J = 6.9 Hz, 2H), 3.88 (s, 3H), 3.19 (sep, J = 6.6 Hz, 1H), 3.07 (sep, J = 5.7 Hz, 1H), 2.51-2.11 (m, 3H), 1.70-0.81 (m, 30H), 0.68 (dd, J = 14.7, 7.2 Hz, 3H), -0.33 (dd, J
= 12.9, 7.8 Hz, 3H). 13C{1H} NMR (d8-THF, δ): 155.2, 149.4 (d, J = 45.1 Hz), 148.1 (d, J
= 15.7 Hz), 144.8 (d, J = 43.9 Hz), 142.4 (d, J = 13.2 Hz), 140.8, 137.3 (d, J = 17.3 Hz), 136.2 (d, J = 18.6 Hz), 134.2 (m), 132.7, 132.1 (d, J = 17.1 Hz), 131.1, 130.8, 130.3, 129.8, 129.1, 126.2, 116.0 (br), 90.9, 84.9, 81.8, 81.3, 81.2, 57.6, 56.6 (br), 35.9 (d, J = 29.2 Hz), 33.5 (d, J = 12.4 Hz), 32.3 (J = 18.9 Hz), 31.0, 30.4, 28.3, 27.9, 27.2, 24.4, 23.8,
23.4, 23.0, 21.4, 20.8, 20.0, 17.8, 17.7, 16.3, 2.2. 31P{1H} NMR (d8-THF, δ): 85.4 (d, J = 28.3 Hz), 73.9 (d, J = 28.3 Hz), 32.4.
Synthesis of [SiPiPr3]Ru(NAr) (Ar = C6H4OMe, 5.5-OMe). {[SiPiPr3]Ru(NAr)}PF6 (Ar
= C6H4OMe, 7-OMe) (11 mg, 0.011 mmol) was dissolved in 4 mL THF and cooled to
−78 oC. CoCp2 (2.0 mg, 0.011 mmol) was added in one portion and the resulting solution was stirred at −78 oC for 15 min The solution was warmed to room temperature and stirred for an additional 15 min The solution was concentrated, and the product was extracted into pentane. The pentane solution was filtered through celite. The extraction process was repeated once more to yield red/brown 5.5-OMe (4.6 mg, 52%). 1H NMR (C6D6, δ): 9.0, 7.8, 6.8, 5.9, 4.0 (extending from 8 to 0 ppm). μeff (Evan’s Method, C6D6/C6H6) = 1.5 B. UV-VIS(in THF): (nm, ε [mol-1 cm-1]), 473 (4200), 737 (1700).
Synthesis of {[SiPiPr3]RuCl}PF6 (5.12). [SiPiPr3]RuCl (30 mg, 0.040 mmol) was dissolved in 6 mL THF. AgPF6 (10 mg, 0.040 mmol) was dissolved in 1 mL THF. Both were cooled to −78 oC and the AgPF6 solution was added to the [SiPiPr3]RuCl solution. A gradual color change from red to brown took place. The solution was stirred at −78 oC for 15 min and was subsequently stirred at room temperature for 30 min The mixture was filtered through celite, and the filtrate was concentrated. The residues were washed with ether and benzene, and the product was extracted into THF and filtered through celite.
Concentration of the purple filtrate yielded 5.12 (22 mg, 61%). 1H NMR (CD2Cl2, δ): 12 (extending from 16 to 8 ppm), 9.7, 6.7, 6.4. μeff (Evan’s Method, CD2Cl2) = 1.73 μB. UV-VIS(in CH2Cl2): (nm, ε [mol-1 cm-1]), 454 (290), 494 (1300). Anal. Calcd for C36H54F6SiP4RuCl: C, 48.62; H, 6.12; N, 0. Found: C, 47.95; H, 6.05; N, 0.00.
Preparation of EPR samples for detecting Ru(I) azide adducts, 5.11-R. A solution of [SiPiPr3]Ru(N2) (0.7 mg in 0.1 mL 2-MeTHF) was added to an EPR tube and the solution was frozen inside the glovebox using the glovebox cold well. A solution of azide (>30 equivalents in 0.1 mL 2-MeTHF) was layered above the frozen [SiPiPr3]Ru(N2) solution and also frozen. The tube was quickly taken out of the glovebox, and immersed in liquid nitrogen. The tube was immersed in a dry ice/isopropanol bath quickly to thaw the solution, and the tube was rapidly shaken to homogenize the solution. The tube was reimmersed in liquid nitrogen and frozen, and was placed inside the EPR cavity for measurement. For detecting 5.11-OMe, several freeze-pump-thaw cycles were additionally applied to remove N2 to favor formation of 5.11-OMe.