Organometallics
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Calcd for C41H39Cl2N4PRu: C, 62.28; H, 4.97; N, 7.09. Found: C,
62.57; H, 5.06; N, 6.87.
(m, 6H), 7.05−6.87 (m, 12H), 5.18 (d, J = 24.6 Hz, 2H). 13C{1H}
NMR (150 MHz, CDCl3): δ 161.5, 160.5, 158.1, 154.5, 154.0, 139.8,
138.4, 135.6, 133.1, 132.9, 132.8, 131.9, 131.2, 130.9, 130.5, 130.3,
129.3, 129.2, 129.0, 128.5, 128.4, 128.3, 128.0, 127.9, 127.3, 127.0,
126.4, 125.5, 121.3, 120.3, 76.2, 72.2. 31P{1H} NMR (243 MHz,
CDCl3): δ 36.7 (s, PPh3). IR (KBr pellets, cm−1) ν: 3057, 1573, 1481,
1434, 1369, 1173, 1087, 1068, 742, 696, 616, 583, 522, 500. HRMS
(ESI-TOF) m/z: [M − 2Cl−]2+ calcd for C49H38BrN4O2PRuS,
479.0335; found, 479.0339. Anal. Calcd for C49H38BrCl2N4O2PRuS:
C, 57.15; H, 3.72; N, 5.44. Found: C, 56.96; H, 3.73; N, 5.08.
Ru Complex 2h. Purple solid. Yield: 0.19 g, 47%. mp 206−208 °C.
1H NMR (600 MHz, CDCl3): δ 9.21 (d, J = 4.9 Hz, 1H), 8.48 (d, J =
8.1 Hz, 1H), 8.01 (d, J = 8.3 Hz, 2H), 7.88−7.76 (m, 3H), 7.68 (d, J
= 8.1 Hz, 1H), 7.57−7.52 (m, 1H), 7.51−7.48 (m, 2H), 7.44 (d, J =
8.1 Hz, 1H), 7.29−7.24 (m, 4H), 7.21−7.18 (m, 1H), 7.17−7.09 (m,
8H), 7.01−6.87 (m, 11H), 5.28 (d, J = 11.3 Hz, 2H). 13C{1H} NMR
(150 MHz, CDCl3): δ 161.2, 160.5, 158.0, 154.4, 154.1, 151.2, 139.2,
138.4, 137.8, 135.8, 132.83, 132.77, 131.0, 130.7, 130.2, 129.5, 129.3,
129.1, 128.53, 128.46, 128.44, 128.1, 128.04, 127.96, 127.4, 127.2,
126.6, 125.4, 124.8, 121.4, 120.4, 75.7, 72.2. 31P{1H} NMR (243
MHz, CDCl3): δ 36.4 (s, PPh3). IR (KBr pellets, cm−1) ν: 3055, 3025,
1603, 1528, 1480, 1434, 1372, 1346, 1312, 1176, 1086, 849, 738, 694,
680, 625, 584, 522, 499. HRMS (ESI-TOF) m/z: [M − 2Cl−]2+ calcd
for C49H38N5O4PRuS, 462.5708; found, 462.5712. Anal. Calcd for
C49H38Cl2N5O4PRuS: C, 59.10; H, 3.85; N, 7.03. Found: C, 59.44; H,
3.90; N, 6.75.
Ru Complex 2c. Purple solid. Yield: 0.22 g, 66%. mp >300 °C. 1H
NMR (400 MHz, CDCl3): δ 9.33 (d, J = 5.3 Hz, 1H), 7.77 (d, J = 7.8
Hz, 1H), 7.57−7.49 (m, 2H), 7.48−7.42 (m, 6H), 7.39 (d, J = 7.4 Hz,
2H), 7.31 (t, J = 7.4 Hz, 2H), 7.23−7.16 (m, 5H), 7.14−7.08 (m,
8H), 6.98 (d, J = 7.7 Hz, 1H), 6.90−6.81 (m, 2H), 6.35 (d, J = 7.7
Hz, 1H), 4.84−4.75 (m, 1H), 4.57−4.45 (m, 1H), 3.85−3.73 (m,
2H), 3.12−3.01 (m, 1H), 2.35 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3): δ 163.3, 161.1, 158.2, 153.9, 153.4, 139.3, 139.2, 137.3,
134.6, 133.1, 133.0, 132.7, 132.3, 130.2, 129.4, 129.0, 128.5, 127.8,
127.7, 126.3, 126.1, 125,8, 124.2, 121.5, 120.4, 67.1, 61.3, 41.6, 21.1.
31P{1H} NMR (162 MHz, CDCl3): δ 43.2 (s, PPh3). IR (KBr pellets,
cm−1) ν: 3054, 2861, 1603, 1551, 1525, 1511, 1482, 1430, 1374,
1293, 1157, 1091, 1039, 827, 777, 754, 744, 697, 527, 514, 496.
HRMS (ESI-TOF) m/z: [M − 2Cl]2+ calcd for C45H39N4PRu,
384.0973; found, 384.0987. Anal. Calcd for C45H39Cl2N4PRu: C,
64.44; H, 4.69; N, 6.68. Found: C, 64.25; H, 5.00; N, 6.39.
Ru Complex 2d. Purple solid. Yield: 0.17 g, 45%. mp 215−216 °C.
1H NMR (600 MHz, CDCl3): δ 9.16 (d, J = 5.4 Hz, 1H), 8.61 (d, J =
8.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.71−7.64 (m, 3H), 7.51−7.42
(m, 3H), 7.32 (t, J = 7.6 Hz, 2H), 7.26−7.23 (m, 5H), 7.18−7.11 (m,
9H), 7.07−6.89 (m, 12H), 5.09 (d, J = 32.4 Hz, 2H). 13C{1H} NMR
(150 MHz, CDCl3): δ 161.5, 160.5, 158.2, 154.5, 153.9, 140.2, 138.6,
135.5, 134.6, 133.4, 132.9, 132.8, 131.4, 131.1, 129.8, 129.3, 129.2,
129.0, 128.9, 128.5, 128.2, 128.1, 127.94, 127.88, 127.6, 127.0, 126.3,
125.7, 121.3, 120.4, 72.1. 31P{1H} NMR (243 MHz, CDCl3): δ 36.9
(s, PPh3). IR (KBr pellets, cm−1) ν: 3055, 3029, 1601, 1584, 1496,
1480, 1447, 1434, 1366, 1298, 1171, 1084, 747, 690, 598, 569, 520,
511, 495. HRMS (ESI-TOF) m/z: [M − 2Cl−]2+ calcd for
C49H39N4O2PRuS, 440.0782; found, 440.0789. Anal. Calcd for
C49H39Cl2N4O2PRuS: C, 61.89; H, 4.13; N, 5.89. Found: C, 62.25;
H, 4.21; N, 5.64.
General Procedure for α-Alkylation of Arylmethyl Nitriles.
In a two-necked 15 mL Schlenk tube were dissolved pincer Ru
catalyst 2h (1.5 mol %), KOH (0.15 equiv), arylmethyl nitriles (0.5
mmol), and alcohol (1.0 mmol) in toluene (0.8 mL). The reaction
mixture was stirred at 140 °C for 4 h. After removal of the solvent, the
residue was purified by TLC on silica gel plates using PE/EA = 20−
30/1 as the eluent to afford the corresponding products 5.
2-(4-Bromophenyl)-3-phenylpropanenitrile (5a). White solid.
Ru Complex 2e. Purple solid. Yield: 0.20 g, 51%. mp 206−208 °C.
1H NMR (600 MHz, CDCl3): δ 9.17 (d, J = 5.5 Hz, 1H), 8.56 (d, J =
8.0 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.54
(d, J = 8.0 Hz, 2H), 7.48−7.39 (m, 2H), 7.33 (d, J = 7.5 Hz, 2H),
7.26−7.22 (m, 3H), 7.19−7.11 (m, 9H), 7.07 (d, J = 8.0 Hz, 2H),
7.04−6.89 (m, 12H), 5.17−5.09 (m, 2H), 2.32 (s, 3H). 13C{1H}
NMR (150 MHz, CDCl3): δ 161.8, 160.4, 158.2, 154.6, 153.9, 145.6,
140.2, 138.5, 137.2, 135.5, 132.9, 132.8, 131.4, 131.1, 130.5, 130.2,
129.3, 129.2, 128.9, 128.5, 128.1, 128.0, 127.93, 127.87, 127.7, 126.7,
126.3, 125.7, 121.4, 120.4, 76.5, 72.0, 21.7. 31P{1H} NMR (243 MHz,
CDCl3): δ 37.0 (s, PPh3). IR (KBr pellets, cm−1) ν: 3053, 3029, 1596,
1480, 1434, 1365, 1301, 1169, 1087, 772, 743, 694, 670, 662, 595,
520, 499. HRMS (ESI-TOF) m/z: [M − 2Cl−]2+ calcd for
C50H41N4O2PRuS, 447.0860; found, 447.0864. Anal. Calcd for
C50H41Cl2N4O2PRuS: C, 62.24; H, 4.28; N, 5.81. Found: C, 62.56;
H, 4.41; N, 5.45.
Ru Complex 2f. Purple solid. Yield: 0.19 g, 49%. mp 222−224 °C.
1H NMR (600 MHz, CDCl3): δ 9.20 (d, J = 5.6 Hz, 1H), 8.58 (d, J =
8.1 Hz, 1H), 7.81 (d, J = 8.1 Hz, 1H), 7.65 (d, J = 7.9 Hz, 1H), 7.56
(d, J = 8.8 Hz, 2H), 7.50 (t, J = 7.6 Hz, 1H), 7.44 (t, J = 8.0 Hz, 1H),
7.38−7.33 (m, 2H), 7.26−7.22 (m, 3H), 7.19−7.11 (m, 9H), 7.06−
6.90 (m, 12H), 6.71 (d, J = 8.8 Hz, 2H), 5.17−5.10 (m, 2H), 3.81 (s,
3H). 13C{1H} NMR (150 MHz, CDCl3): δ 164.4, 162.0, 160.4, 158.3,
154.7, 154.0, 140.3, 138.7, 135.4, 132.9, 132.8, 131.4, 131.14, 131.08,
129.3, 129.2, 128.9, 128.6, 128.1, 128.0, 127.94, 127.88, 127.7, 126.9,
126.3, 125.7, 124.7, 121.2, 120.3, 115.1, 76.5, 72.0, 55.6. 31P{1H}
NMR (243 MHz, CDCl3): δ 37.0 (s, PPh3). IR (KBr pellets, cm−1) ν:
3054, 3028, 1736, 1593, 1576, 1495, 1481, 1435, 1364, 1262, 1163,
1088, 1025, 743, 694, 672, 600, 553, 520, 499. HRMS (ESI-TOF) m/
z: [M − 2Cl−]2+ calcd for C50H41N4O3PRuS, 455.0835; found,
455.0842. Anal. Calcd for C50H41Cl2N4O3PRuS: C, 61.22; H, 4.21; N,
5.71. Found: C, 60.84; H, 4.34; N, 5.46.
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Yield: 119 mg, 83%. mp 80−81 °C. H NMR (400 MHz, CDCl3):
δ 7.52−7.43 (m, 2H), 7.33−7.26 (m, 3H), 7.14−7.06 (m, 4H), 3.97
(t, J = 7.0 Hz, 1H), 3.18 (dd, J = 13.4, 7.7 Hz, 1H), 3.09 (dd, J = 13.4,
6.7 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 135.8, 134.1,
132.2, 129.2, 128.7, 127.6, 122.3, 119.9, 42.0, 39.2. HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C15H13BrN, 286.0226; found,
286.0228.
2-(4-Methoxyphenyl)-3-phenylpropanenitrile (5b). White solid.
1
Yield: 107 mg, 90%. mp 63−64 °C. H NMR (600 MHz, CDCl3): δ
7.33−7.22 (m, 3H), 7.14 (dd, J = 8.0, 19.7 Hz, 4H), 6.86 (d, J = 8.0
Hz, 2H), 3.94 (t, J = 8.0 Hz, 1H), 3.80 (s, 3H), 3.16 (dd, J = 13.2, 8.4
Hz, 1H), 3.09 (dd, J = 13.6, 6.5 Hz, 1H). 13C{1H} NMR (150 MHz,
CDCl3): δ 159.4, 136.5, 129.3, 128.65, 128.61, 127.3, 127.2, 120.6,
114.4, 55.3, 42.3, 39.0. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H15NNaO, 260.1046; found, 260.1048.
2-(4-(tert-Butyl)phenyl)-3-phenylpropanenitrile (5c). White solid.
Yield: 55 mg, 42%. mp 124−125 °C. 1H NMR (400 MHz, CDCl3): δ
7.41−7.35 (m, 2H), 7.34−7.26 (m, 3H), 7.24−7.14 (m, 4H), 3.97
(dd, J = 8.6, 6.4 Hz, 1H), 3.21−3.07 (m, 2H), 1.32 (s, 9H). 13C{1H}
NMR (100 MHz, CDCl3): δ 151.3, 136.6, 132.3, 129.2, 128.7, 127.3,
127.1, 126.0, 120.5, 42.3, 39.5, 34.6, 31.3. HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C19H22N, 264.1747; found, 264.1749.
3-Phenyl-2-(p-tolyl)propanenitrile (5d). White solid. Yield: 100
1
mg, 90%. mp 71−73 °C. H NMR (400 MHz, CDCl3): δ 7.33−7.23
(m, 3H), 7.19−7.08 (m, 6H), 3.96 (dd, J = 8.4, 6.4 Hz, 1H), 3.17 (dd,
J = 13.7, 8.4 Hz, 1H), 3.10 (dd, J = 13.7, 6.4 Hz, 1H), 2.35 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 138.0, 136.5, 132.3, 129.7,
129.2, 128.6, 127.3, 120.6, 42.3, 39.5, 21.1. HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C16H16N, 222.1277; found, 222.1278.
2,3-Diphenylpropanenitrile (5e). White solid. Yield: 99 mg, 95%.
1
mp 52−53 °C. H NMR (400 MHz, CDCl3): δ 7.41−7.19 (m, 8H),
7.17−7.07 (m, 2H), 3.98 (dd, J = 8.4, 6.4 Hz, 1H), 3.17 (dd, J = 13.6,
8.1 Hz, 1H), 3.11 (dd, J = 13.6, 6.6 Hz, 1H). 13C{1H} NMR (100
MHz, CDCl3): δ 136.3, 135.3, 129.3, 129.1, 128.7, 128.2, 127.5,
127.4, 120.4, 42.2, 39.8. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C15H14N, 208.1121; found, 208.1123.
Ru Complex 2g. Purple solid. Yield: 0.19 g, 47%. mp 218−220 °C.
1H NMR (600 MHz, CDCl3): δ 9.24−9.15 (m, 1H), 8.52 (d, J = 8.0
Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 7.51−
7.46 (m, 3H), 7.44−7.35 (m, 5H), 7.26−7.22 (m, 6H), 7.18−7.11
G
Organometallics XXXX, XXX, XXX−XXX