Organometallics
Article
82.84, 82.43, 80.64, 30.38, 22.43, 21.96, 19.93, 18.46. Anal. Calcd for
C23H25N2ORuCl: C 57.32, H 5.23, N 5.81. Found: C 57.39, H 5.17, N
5.88. MS (MALDI-TOF): calcd for C23H25N2ORu+ [M − Cl]+
447.101, found 447.088. IR (KBr, cm−1): 3012(w), 2920(s),
2838(w), 1619(vs), 1584(s), 1455(s), 1433(s), 1279(s), 1151(vs),
892(s), 834(m), 740(m), 600(s), 529(s).
47.25, H 3.96, N 5.51. Found: C 47.22, H 3.95, N 5.58. MS (MALDI-
TOF): calcd for C20H20ClN2ORuS+ [M − Cl]+ 473.002 (M+), found
473.003. IR (KBr, cm−1): 3048(w), 2967(s), 2908(w), 2873(s),
1610(vs), 1514(s), 1455(s), 1432(s), 1385(s), 1326(s), 1162(vs),
1067(s), 985(s), 881(s), 822(s), 705(m), 656(m), 566(m).
Half-Sandwich Ruthenium Complex 2g. Yield: 171.2 mg, 62%. 1H
NMR (300 MHz, CDCl3): δ 8.09 (s, 1H), 7.58 (d, J = 6.0 Hz, 1H),
7.28 (t, 1H), 7.26 (t, 1H), 7.13 (d, J = 3.0 Hz, 1H), 6.88 (d, J = 9.0 Hz,
1H), 5.38 (m, 2H), 5.28 (d, J = 6.0 Hz, 1H), 4.74 (d, J = 6.0 Hz, 1H),
2.71 (t, 1H), 2.16 (s, 3H), 1.16 (d, 6H). 13C NMR (125 MHz,
CDCl3): δ 176.58, 166.98, 164.91, 139.56, 139.04, 137.26, 125.98,
120.76, 120.02, 105.94, 102.93, 99.68, 85.80, 82.97, 82.37, 82.19,
30.93, 22.77, 22.50, 18.99. Anal. Calcd for C20H20BrN2ORuSCl: C
43.45, H 3.65, N 5.07. Found: C 43.47, H 3.61, N 5.01. MS (MALDI-
TOF): calcd for C20H20BrN2ORuS+ [M − Cl]+ 516.952, found
516.954. IR (KBr, cm−1): 3077(w), 3041(s), 2932(w), 2850(s),
1618(vs), 1583(s), 1555(s), 1491(s), 1428(s), 1273(s), 1171(vs),
1145(s), 990(s), 872(s), 740(s), 644(m), 580(m), 525(m).
Half-Sandwich Ruthenium Complex 2b. Yield: 188.4 mg, 75%. 1H
NMR (300 MHz, CDCl3): δ 8.50 (d, J = 6.0 Hz, 1H), 8.10 (d, J = 9.0
Hz, 1H), 7.95 (s, 1H), 7.80 (d, J = 6.0 Hz, 1H), 7.32 (t, 1H), 7.15 (t,
1H), 6.98 (m, 1H), 6.96 (d, J = 9.0 Hz, 1H), 5.38 (d, J = 6.0 Hz, 1H),
5.26 (d, J = 6.0 Hz, 1H), 5.15 (d, J = 6.0 Hz, 1H), 4.43 (d, J = 3.0 Hz,
1H), 2.65 (m, 1H), 2.08 (s, 3H), 1.12 (d, 6H). 13C NMR (75 MHz,
CDCl3): δ 166.68, 164.64, 163.83, 147.81, 138.12, 135.78, 133.71,
124.68, 122.83, 121.13, 118.85, 118.38, 102.11, 98.21, 85.38, 83.06,
82.34, 80.83, 30.42, 22.40, 21.93, 18.48. Anal. Calcd for
C22H22ClN2ORuCl: C 52.60, H 4.41, N 5.58. Found: C 52.54, H
4.44, N 5.53. MS (MALDI-TOF): calcd for C22H22ClN2ORu+ [M −
Cl]+ 467.046, found 467.047. IR (KBr, cm−1): 3077(w), 3041(s),
2932(w), 2850(s), 1628(vs), 1583(s), 1555(s), 1491(s), 1428(s),
1273(s), 1181(vs), 1145(s), 990(s), 872(s), 740(m), 644(m), 580(s),
525(s).
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Half-Sandwich Ruthenium Complex 2h. Yield: 99.6 mg, 45%. H
NMR (300 MHz, CDCl3): δ 8.18 (s, 1H), 7.57 (d, J = 3.0 Hz, 1H),
7.26 (t, 2H), 7.01 (t, 2H), 6.46 (t, 1H), 5.39 (m, 2H), 5.28 (d, J = 6.0
Hz, 1H), 4.75 (d, J = 6.0 Hz, 1H), 2.74 (m, 1H), 2.16 (s, 3H), 1.15 (d,
6H). 13C NMR (75 MHz, CDCl3): δ 176.71, 167.64, 165.37, 138.49,
136.78, 136.01, 123.56, 120.20, 118.31, 115.05, 102.26, 99.09, 85.34,
82.52, 82.00, 81.59, 30.50, 22.41, 22.08, 18.64. Anal. Calcd for
C20H21N2ORuSCl: C 50.68, H 4.47, N 5.91. Found: C 50.60, H 4.43,
N 5.98. MS (MALDI-TOF): calcd for C20H21N2ORuS+ [M − Cl]+
439.041, found 439.042. IR (KBr, cm−1): 3083(w), 2967(s), 2908(w),
2861(s), 1607(vs), 1514(s), 1443(s), 1373(s), 1326(s), 1173(vs),
1127(s), 1057(s), 881(s), 822(s), 732(s), 694(m), 576(s).
Half-Sandwich Ruthenium Complex 2c. Yield: 183.0 mg, 67%. 1H
NMR (300 MHz, CDCl3): δ 8.50 (d, J = 6.0 Hz, 1H), 8.09 (d, J = 9.0
Hz, 1H), 7.94 (s, 1H), 7.80 (t, 1H), 7.32 (d, J = 6.0 Hz, 1H), 7.28(t,
1H), 7.13 (s, 1H), 6.91 (d, J = 9.0 Hz, 1H), 5.38 (d, J = 6.0 Hz, 1H),
5.26 (d, J = 6.0 Hz, 1H), 5.15 (d, J = 3.0 Hz, 1H), 4.44(d, J = 6.0 Hz,
1H), 2.62 (t, 1H), 2.08 (s, 3H), 1.12 (d, 6H). 13C NMR (125 MHz,
CDCl3): δ 167.07, 165.35, 164.20, 148.21, 138.73, 138.52, 137.32,
125.48, 123.22, 121.49, 120.18, 105.45, 102.57, 98.62, 85.75, 83.48,
82.73, 81.28, 30.82, 22.78, 22.34, 18.85. Anal. Calcd for
C22H22BrN2ORuCl: C 48.32, H 4.05, N 5.12. Found: C 48.36, H
4.12, N 5.16. MS (MALDI-TOF): calcd for C22H22BrN2ORu+ [M −
Cl]+ 510.995, found 510.998. IR (KBr, cm−1): 3050(s), 2932(s),
2850(s), 1608(s), 1580(s), 1555(s), 1373(s), 1273(s), 1181(s),
990(s), 817(s), 790(m), 735(m), 635(w).
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Half-Sandwich Ruthenium Complex 2i. Yield: 180.3 mg, 67%. H
NMR (300 MHz, CDCl3): δ 8.25 (s, 1H), 8.01 (d, J = 9.0 Hz, 1H),
7.84 (d, J = 9.0 Hz, 1H), 7.56 (t, 1H), 7.44 (m, 1H), 7.12 (d, J = 9.0
Hz, 1H), 6.94 (d, J = 9.0 Hz, 1H), 6.81 (m, 1H), 5.39 (s, 2H), 5.29 (s,
1H), 4.80 (d, J = 6.0 Hz, 1H), 2.80 (m, 1H), 2.23 (s, 3H), 2.14 (s,
3H), 1.17 (d, 6H). 13C NMR (75 MHz, CDCl3): δ 167.06, 164.48,
164.29, 147.70, 137.95, 137.74, 134.77, 128.43, 125.10, 123.10, 122.78,
122.45, 121.39, 117.84, 101.76, 97.99, 85.28, 82.84, 82.43, 80.64,
30.38, 22.43, 21.96, 19.93, 18.46. Anal. Calcd for C25H25N2ORuSCl: C
55.81, H 4.68, N 5.21. Found: C 55.83, H 4.75, N 5.19. MS (MALDI-
TOF): calcd for C25H25N2ORuS+ [M − Cl]+ 503.073, found 503.071.
IR (KBr, cm−1): 3048(w), 2978(w), 2873(w), 1730(w), 1601(vs),
1573(s), 1514(s), 1443(s), 1396(s), 1314(s), 1127(vs), 1057(s),
881(s), 822(s), 753(m), 670(m), 630(m).
Half-Sandwich Ruthenium Complex 2d. Yield: 105.4 mg, 45%. 1H
NMR (300 MHz, CDCl3): δ 8.49 (d, J = 6.0 Hz, 1H), 8.13 (d, J = 9.0
Hz, 1H), 8.02 (s, 1H), 7.78 (m, 1H), 7.29 (t, 1H), 7.21 (d, J = 9.0 Hz,
1H), 7.01 (d, J = 9.0 Hz, 2H), 6.43 (t, 1H), 5.37 (d, J = 6.0 Hz, 1H),
5.25 (d, J = 6.0 Hz, 1H), 5.14 (d, J = 6.0 Hz, 1H), 4.45 (d, J = 6.0 Hz,
1H), 2.64 (m, 1H), 2.07 (s, 3H), 1.10 (d, 6H). 13C NMR (75 MHz,
CDCl3): δ 166.89, 165.97, 164.68, 147.73, 138.03, 135.91, 135.88,
123.04, 122.60, 121.32, 118.41, 114.49, 101.90, 98.00, 85.26, 82.95,
82.40, 80.67, 30.38, 22.42, 21.90, 18.47. Anal. Calcd for
C22H23N2ORuCl: C 56.47, H 4.95, N 5.99. Found: C 56.50, H 4.90,
N 6.05. MS (MALDI-TOF): calcd for C22H23N2ORu+ [M − Cl]+
433.085, found 433.082. IR (KBr, cm−1): 3059(w), 2922(s), 2840(w),
1612(vs), 1580(s), 1550(s), 1464(s), 1428(s), 1281(vs), 1181(s),
1145(s), 999(s), 835(s), 790(m), 762(s), 580(m), 535(m).
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Half-Sandwich Ruthenium Complex 2j. Yield: 195.4 mg, 70%. H
NMR (300 MHz, CDCl3): δ 8.24 (s, 1H), 8.02 (d, J = 6.0 Hz, 1H),
7.85 (d, J = 6.0 Hz, 1H), 7.57 (t, 1H), 7.46 (t, 1H), 7.19 (d, J = 9.0 Hz,
1H), 7.03 (s, 1H), 6.96 (d, J = 9.0 Hz, 1H), 5.40 (s, 2H), 5.29 (s, 1H),
4.79 (d, J = 6.0 Hz, 1H), 2.77 (t, 1H), 2.23 (s, 3H), 1.17 (d, 6H). 13C
NMR (75 MHz, CDCl3): δ 175.38, 164.65, 161.72, 149.20, 137.11,
133.80, 126.76, 125.61, 125.36, 123.58, 123.14, 121.68, 119.10, 118.54,
102.55, 99.74, 85.76, 82.59, 82.00, 81.88, 30.60, 22.37, 22.26, 18.76.
Anal. Calcd for C24H22ClN2ORuSCl: C 51.62, H 3.97, N 5.02. Found:
C 51.65, H 3.94, N 4.98. MS (MALDI-TOF): calcd for
C24H22ClN2ORuS+ [M − Cl]+ 523.018, found 523.015. IR (KBr,
cm−1): 3050(w), 2959(s), 2913(w), 2867(s), 1607(vs), 1573(s),
1510(s), 1436(s), 1373(s), 1318(s), 1136(vs), 1072(s), 817(s),
744(m), 690(m).
Half-Sandwich Ruthenium Complex 2e. Yield: 136.7 mg, 56%. 1H
NMR (300 MHz, CDCl3): δ 8.11 (s, 1H), 7.57 (d, J = 3.0 Hz, 1H),
7.25 (s, 1H), 7.09 (d, J = 9.0 Hz, 1H), 6.93 (d, J = 9.0 Hz, 1H), 6.78
(s, 1H), 5.35 (s, 2H), 5.29 (t, 1H), 4.75 (d, J = 6.0 Hz, 1H), 2.72 (m,
1H), 2.16 (s, 3H), 2.14 (s, 3H), 1.15 (d, 6H). 13C NMR (75 MHz,
CDCl3): δ 166.09, 165.09, 138.80, 138.47, 134.61, 132.88, 123.71,
123.29, 119.99, 117.75, 110.00, 99.05, 85.34, 82.43, 82.03, 81.59,
30.50, 22.42, 22.13, 19.94, 18.63. Anal. Calcd for C21H23N2ORuSCl: C
51.69, H 4.75, N 5.74. Found: C 51.72, H 4.73, N 5.79. MS (MALDI-
TOF): calcd for C21H23N2ORuS+ [M − Cl]+ 453.057, found 453.057.
IR (KBr, cm−1): 3083(w), 2967(w), 2920(w), 2861(s), 1607(vs),
1501(s), 1443(s), 1412(s), 1385(s), 1326(s), 1173(vs), 1138(s),
1068(s), 869(s), 822(m), 681(m), 563(m).
Half-Sandwich Ruthenium Complex 2k. Yield: 216.8 mg, 72%. 1H
NMR (300 MHz, CDCl3): δ 8.22 (s, 1H), 8.02 (d, J = 9.0 Hz, 1H),
7.85 (d, J = 9.0 Hz, 1H), 7.57 (t, 1H), 7.45 (t, 1H), 7.29 (m, 1H), 7.17
(d, J = 3.0 Hz, 1H), 6.90 (d, J = 9.0 Hz, 1H), 5.40 (s, 2H), 5.30 (d, J =
6.0 Hz, 1H), 4.79 (d, J = 6.0 Hz, 1H), 2.79 (m, 1H), 2.23 (s, 3H), 1.17
(d, 6H). 13C NMR (125 MHz, CDCl3): δ 175.33, 166.90, 164.63,
149.20, 139.59, 137.08, 126.77, 125.71, 125.63, 123.15, 121.68, 119.47,
111.31, 105.75, 102.56, 99.76, 85.76, 82.60, 81.99, 81.90, 30.60, 22.37,
22.26, 18.76. Anal. Calcd for C24H22BrN2ORuSCl: C 47.81, H 3.68, N
4.65. Found: C 47.73, H 3.65, N 4.70. MS (MALDI-TOF): calcd for
C24H22BrN2ORuS+ [M − Cl]+ 566.968, found 566.968. IR (KBr,
cm−1): 3048(w), 2976(s), 2920(w), 2849(s), 1630(vs), 1572(s),
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Half-Sandwich Ruthenium Complex 2f. Yield: 178.0 mg, 70%. H
NMR (300 MHz, CDCl3): δ 8.10 (s, 1H), 7.58 (d, J = 3.0 Hz, 1H),
7.28 (t, 1H), 7.17 (m, 1H), 6.98 (d, J = 3.0 Hz, 1H), 6.94 (d, J = 9.0
Hz, 1H), 5.38 (m, 2H), 5.28 (d, J = 6.0 Hz, 1H), 4.74 (d, J = 6.0 Hz,
1H), 2.71 (m, 1H), 2.16 (s, 3H), 1.16 (d, 6H). 13C NMR (75 MHz,
CDCl3): δ 176.25, 166.23, 164.53, 138.63, 136.70, 133.63, 125.20,
120.47, 118.94, 118.68, 102.46, 99.31, 85.42, 82.58, 81.95, 81.75,
30.53, 22.39, 22.11, 18.64. Anal. Calcd for C20H20ClN2ORuSCl: C
G
Organometallics XXXX, XXX, XXX−XXX