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C6H4), 7.92 (d, J = 7 Hz, 2H, C6H4). [Note: Due to the very poor (s, 1H, Ru–H), 0.90 (d, J = 7 Hz, 3H, CH3 of iPr), 1.00 (d, J =
solubility of 3a, decent 13C NMR spectrum was not obtained.] 7 Hz, 3H, CH3 of iPr), 1.68 (s, 3H, CH3), 1.91 (sept, J = 7 Hz,
Anal. Calcd for C28H28ClF6N3O3RuS (737.12): C, 45.62; H, 3.83; 1H, CH of iPr), 2.18 (s, 6H, CH3), 2.21 (s, 3H, CH3), 3.63 (s, 3H,
N, 5.70. Found: C, 45.65; H, 3.81; N, 5.72. 4a: 1H NMR N–CH3), 4.27 (d, J = 6 Hz, 1H, Ar–H of p-cymene), 4.54 (d, J =
(CD3CN): δ 1.15 (d, J = 7 Hz, 3H, CH3 of iPr), 1.19 (d, J = 7 Hz, 6 Hz, 1H, Ar–H of p-cymene), 4.65 (d, J = 6 Hz, 1H, Ar–H of
3H, CH3 of iPr), 2.00 (s, 3H, CH3), 2.66 (sept, J = 7 Hz, 1H, CH p-cymene), 5.42 (d, J = 6 Hz, 1H, Ar–H of p-cymene), 5.86
of iPr), 3.82 (s, 3H, N–CH3), 5.27 (d, J = 6 Hz, 1H, Ar–H of (broad-s, 2H, CH2), 6.83 (s, 2H, C6H2), 7.43–7.51 (m, 3H,
p-cymene), 5.31 (d, J = 6 Hz, 1H, Ar–H of p-cymene), 5.64 (d, J = C6H5), 7.57–7.66 (m, 2H, C6H5). 13C NMR (CD2Cl2): δ 18.87
6 Hz, 1H, Ar–H of p-cymene), 5.66 (d, J = 6 Hz, 1H, Ar–H of (CH3), 20.34 (CH3), 21.18 (CH3), 23.09 (CH3), 23.82 (CH3),
p-cymene), 5.73 (d, J = 14 Hz, 1H, CH of CH2), 6.13 (d, J = 32.01 (CH), 37.52 (N–CH3), 53.65 (CH2), 79.29, 85.01, 85.69,
14 Hz, 1H, CH of CH2), 7.33–7.48 (m, 5H, C6H5), 7.71 (d, J = 88.14, 97.80, 100.91 (Ar–C of p-cymene), 128.81, 129.18,
8 Hz, 2H, C6H4), 7.93 (d, J = 8 Hz, 2H, C6H4). 13C NMR 129.48, 129.69, 130.90, 132.18, 138.43, 139.03, 147.67 (Ar–C),
(CD3CN): δ 18.86 (CH3), 22.38 (CH3), 22.79 (CH3), 31.87 (CH), 169.50 (Ru–C). Anal. Calcd for C29H36ClN3Ru (563.14): C, 61.85;
38.65 (N–CH3), 58.33 (CH2), 83.40, 85.86, 88.59, 90.65, 102.36, H, 6.44; N, 7.46. Found: C, 61.89; H, 6.42; N, 7.45.
111.71 (Ar–C of p-cymene), 126.66, 129.28, 129.36, 129.65,
Synthesis of [PhCH2N2(NMe)C2Ph]RuHCl(p-cymene) (5c)
132.90, 133.35, 136.93, 146.06 (Ar–C), 159.18 (Ru–C). 19F NMR
(CD3CN): δ −63.41, −79.30.
A solution of Et3SiH (0.141 g, 1.20 mmol) in CH2Cl2 (4 mL)
3b and 4b. A mixture of 2b (0.210 g, 0.35 mmol) and was added dropwise to a solution of 2c (0.408 g, 0.73 mmol) in
Me3SiOSO2CF3 (0.087 g, 0.39 mmol) in CH2Cl2 (3 mL) yielded CH2Cl2 (5 mL) at r.t. The reaction mixture was stirred at 45 °C
3b (0.247 g, 91%) as red-brown crystals. 3b was dissolved in for 2 h resulting in a yellow-brown solution. All volatiles were
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CD3CN to form 4b. 3b: H NMR (CD3OD): δ 1.30 (d, J = 7 Hz, removed from the solution under high vacuum resulting
6H, CH3 of iPr), 2.20 (s, 3H, CH3), 2.30 (s, 3H, CH3), 2.41 in a grey-yellow solid. The solid was washed with pentane
(s, 6H, CH3), 2.78 (sept, J = 7 Hz, 1H, CH of iPr), 4.26 (s, 3H, (3 × 10 mL) and dried under high vacuum to give yellow solid
N–CH3), 5.65 (d, J = 6 Hz, 2H, Ar–H of p-cymene), 5.87 (d, J = as pure product 5b (0.366 g, 96%). X-ray quality crystals were
6 Hz, 2H, Ar–H of p-cymene), 5.90 (s, 2H, CH2), 7.01 (s, 2H, grown by slow diffusion of pentane into a solution of 5b in
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C6H2), 7.60–7.70 (m, 5H, C6H5). 13C NMR (CD3OD): δ 18.91 CH2Cl2. H NMR (CD2Cl2): δ −6.74 (s, 1H, Ru–H), 0.80 (d, J =
(CH3), 19.86 (CH3), 21.13 (CH3), 22.28 (CH3), 32.61 (CH), 39.22 7 Hz, 3H, CH3 of iPr), 0.86 (d, J = 7 Hz, 3H, CH3 of iPr), 1.56 (s,
(N–CH3), 53.11 (CH2), 78.49, 79.28, 79.70, 80.34 (Ar–C of 3H, CH3), 1.77 (sept, J = 7 Hz, 1H, CH of iPr), 3.73 (s, 3H,
p-cymene), 98.44, 102.66, 123.86, 126.37, 129.26, 130.57, N–CH3), 4.20 (d, J = 7 Hz, 1H, Ar–H of p-cymene), 4.47 (d, J =
130.71, 132.82, 139.97, 141.38, 144.87 (Ar–C) [Note: Ru–C was 7 Hz, 1H, Ar–H of p-cymene), 4.49 (d, J = 7 Hz, 1H, Ar–H of
not detected]. Anal. Calcd for C31H34ClF6N3O3RuS (779.20): p-cymene), 5.29 (d, J = 7 Hz, 1H, Ar–H of p-cymene), 5.81 (d, J =
C, 47.78; H, 4.40; N, 5.39. Found: C, 47.74; H, 4.44; N, 5.43. 4b: 14 Hz, 1H, CH2), 6.17 (d, J = 14 Hz, 1H, CH2), 7.19–7.30
1H NMR (CD3CN): δ 1.21 (d, J = 7 Hz, 3H, CH3 of iPr), 1.24 (d, (m, 3H, C6H5), 7.31–7.38 (m, 2H, C6H5), 7.41–7.51 (m, 3H,
J = 7 Hz, 3H, CH3 of iPr), 2.12 (s, 3H, CH3), 2.29 (s, 6H, CH3 of C6H5), 7.58–7.68 (m, 2H, C6H5). 13C NMR (CD2Cl2): δ 18.26
Mes), 2.31 (s, 3H, CH3 of Mes), 2.75 (sept, J = 7 Hz, 1H, CH of (CH3), 22.52 (CH3), 23.18 (CH3), 31.37 (CH), 37.23 (N–CH3),
iPr), 3.67 (s, 3H, N–CH3), 5.36 (d, J = 6 Hz, 1H, Ar–H of 56.89 (CH2), 78.96, 84.58, 85.47, 87.37, 97.56, 100.16 (Ar–C
p-cymene), 5.39 (d, J = 14 Hz, 1H, CH og CH2), 5.55 (d, J = 6 of p-cymene), 127.75, 128.14, 128.40, 129.33, 130.25, 131.74,
Hz, 1H, Ar–H of p-cymene), 5.74 (d, J = 6 Hz, 1H, Ar–H of 136.76, 147.37 (Ar–C), 171.06 (Ru–C). Anal. Calcd for
p-cymene), 5.79 (d, J = 6 Hz, 1H, Ar–H of p-cymene), 6.40 (d, J = C26H30ClN3Ru (521.06): C, 59.93; H, 5.80; N, 8.06. Found:
14 Hz, 1H, CH of CH2), 6.98 (s, 2H, C6H5), 7.40–7.50 (m, 2H, C, 60.02; H, 5.87; N, 8.01.
C6H5), 7.54–7.65 (m, 3H, C6H5). 13C NMR (CD3CN): δ 19.15
(CH3), 20.45 (CH3), 21.11 (CH3), 22.42 (CH3), 23.15 (CH3),
Synthesis of [TripCH2N2(NMe)C2Ph]RuHCl(p-cymene) (5d)
32.01 (CH), 38.22 (N–CH3), 54.04 (CH2), 83.13, 85.45, 88.77, 5d was synthesized following an identical synthetic procedure
90.86, 103.01, 110.75 (Ar–C of p-cymene), 128.47, 129.44, as described for the synthesis of 5c. A mixture of Et3SiH
129.88, 131.04, 131.77, 139.73, 140.08, 147.50 (Ar–C), 155.61 (0.070 g, 0.60 mmol) and 2d (0.341 g, 0.50 mmol) in CH2Cl2
(Ru–C). 19F NMR (CD3CN): δ −79.30.
(8 mL) yielded 5d as a yellow solid (0.311 g, 96%). 1H NMR
(CD2Cl2): δ −6.59 (s, 1H, Ru–H), 0.92 (d, J = 7 Hz, 3H, CH3 of
iPr), 1.01 (d, J = 7 Hz, 3H, CH3 of iPr), 1.09 (d, J = 7 Hz, 3H,
Synthesis of [MesCH2N2(NMe)C2Ph]RuHCl(p-cymene) (5b)
A solution of Et3SiH (0.141 g, 1.20 mmol) in CH2Cl2 (5 mL) CH3 of iPr), 1.11 (d, J = 7 Hz, 3H, CH3 of iPr), 1.20 (d, J = 7 Hz,
was added dropwise to a solution of 2b (0.599 g, 1.00 mmol) in 3H, CH3 of iPr), 1.92 (sept, J = 7 Hz, 1H, CH of iPr), 2.85 (sept,
CH2Cl2 (10 mL) at r.t. The reaction mixture was stirred at r.t. J = 7 Hz, 1H, CH of iPr), 2.98 (sept, J = 7 Hz, 1H, CH of iPr),
for 16 h resulting in a yellow-brown solution. All volatiles were 3.64 (s, 3H, N–CH3), 4.30 (d, J = 7 Hz, 1H, Ar–H of p-cymene),
removed from the solution under high vacuum resulting in a 4.52 (d, J = 7 Hz, 1H, Ar–H of p-cymene), 4.71 (d, J = 7 Hz, 1H,
yellow-brown solid. The solid was washed with hexanes (3 × Ar–H of p-cymene), 5.43 (d, J = 7 Hz, 1H, Ar–H of p-cymene),
10 mL) and dried under high vacuum to give yellow solid as 5.82 (d, J = 14 Hz, 1H, CH2), 6.06 (d, J = 14 Hz, 1H, CH2), 7.01
pure product 5b (0.552 g, 98%). 1H NMR (CD2Cl2): δ −6.60 (s, 2H, C6H2), 7.43–7.51 (m, 3H, C6H5), 7.56–7.64 (m, 2H,
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Dalton Trans., 2014, 43, 15638–15645 | 15643