M. F. Baran et al.
[1,2-b:5,4-b’]dipyridine-2-one,[43] 4,5-diazaflourene,[44] 9,9′-bis(4,5-
diazafluorenyl),[45] 9,9′-bis(4,5-diazafluorenylidene),[46] and N,N′-bis
(cyclopenta[2,1-b:3,4-b’]dipyridine-5-ylidine) hydrazine[47] were pre-
pared as described previously. 1H nuclear magnetic resonance
(NMR) (400.1 MHz) and 13C NMR (100.6 MHz) spectra were
recorded using a Bruker Avance 400 spectrometer, with δ
referenced to external tetramethylsilane. Fourier transfer infrared
(FT-IR) spectra were recorded with a Mattson 1000 ATI UNICAM
FT-IR spectrometer as KBr pellets. A Shimadzu LC MS 8040 LC
MS/MS triple quadrupole instrument was used for mass spectra
analysis due to the inherent characteristics of accurate mass
measurements. The elemental analyses for carbon, hydrogen
and nitrogen were performed with a Costech Combustion System
CHNS-O instrument. Melting points were obtained using a
Gallenkamp apparatus with open capillaries and were uncor-
rected. GC analyses were performed using a Shimadzu GC 2010
Plus equipped with a capillary column (5% biphenyl, 95%
dimethylsiloxane; 30 m × 0.32 mm × 0.25 μm). The GC parameters
for the transfer hydrogenation of ketones were as follows: initial
temperature, 110 °C; initial time, 1 min; solvent delay, 4.48 min;
temperature ramp, 80 °C minÀ1; final temperature, 200 °C; final
time, 21.13 min; injector port temperature, 200 °C; detector
temperature, 200 °C; injection volume, 2.0 μl.
168.93 (C4b), 153.45 (C6), 132.17 (C8), 131.59 (C8a), 130.75 (C7),
128.06 (C1), 118,86 (C2), 112.29 (C9a), 103.26 (C11), 99.44 (C14),
82.57, 82.30 (C12,12′), 81.57, 80.17 (C13,13′), 31.14 (C15), 22.58, 22.09
(C16,17), 18.89 (C10). ESI-MS m/z: 469. Anal. Calcd for
C21H20N2O2RuClPF6 (%): C, 41.09; H, 3.29; N, 4.56. Found (%): C,
40.96; H, 3.19; N, 4.48.
Complex 3
Yield (85%); m.p. 291–294 °C. FT-IR (KBr, cmÀ1): 3524 (νO H), 3093
(aromatic νC H), 2967, 2875 (aliphatic νC H), 1628, 1603, 1472,
1414 (νC N, νC C), 1375 (νC N) 837 (νPF6). 1H NMR (400 MHz,
DMSO-d6, δ, ppm): 1.08 (d, 6H, J = 6.8 Hz, p-cymene H16,17), 2.17 (s,
3H, p-cymene H10), 2.75 (m, 1H, p-cymene H15), 4.17 (s, 2H,
Daf-H9), 5.82 (d, 2H, J = 6.12 Hz, p-cymene H13,13′), 6.24 (d, 2H,
J = 5.9 Hz, p-cymene H12,12′), 6.92 (d, 1H, J = 8.3 Hz, Daf-H2), 7.65
(dd, 1H, J = 7.6 and 5.4 Hz, Daf-H7), 8.0 (d, 1H, J = 8.3 Hz, Daf-H1),
8.21 (d, 1H, J = 7.6 Hz, Daf-H8), 9.11 (d, 1H, J = 5.4 Hz, Daf-H6). 13
C
NMR (100 MHz, DMSO-d6, δ, ppm): 166.54 (C3), 162.33 (C4a),
159.05 (C4b), 151,34 (C6), 139.20 (C1), 137.19 (C8), 136.71 (C8a),
128.09 (C9a), 126.12 (C7), 112.98 (C2), 104.04 (C11), 100.44 (C14),
83.29, 82.49 (C12,12′), 81.44, 80.94 (C13,13′), 36.70 (C9), 31.18 (C15),
22.08 (C16,17), 18.89 (C10). ESI-MS m/z: 455. Anal. Calcd for
C21H20N2ORuClPF6 (%): C, 42.18; H, 3.38; N, 4.69. Found (%): C,
41.82; H, 3.29; N, 4.56.
General procedure for synthesis of ruthenium(II) complexes
Complex 4
[Ru(η[6]-p-cymene)(μ-Cl)Cl]2 (0.5 equiv. for complexes 1–4 or
1 equiv. for complexes 5–7) was added to a solution of ligand
(1 equiv.) in CH2Cl2 (10 ml) and the mixture was stirred at room
temperature for 2 h. The precipitate formed was filtered and
washed with dichloromethane and then dried in a vacuum. The
residue obtained was dissolved in a minimum amount of water,
and a saturated aqueous solution of [NH4][PF6] was then added
dropwise until no more precipitate formed. The mixture was left
to stand for a few hours, after which it was filtered and dried.
Yield (90%); m.p. 224–226 °C. FT-IR (KBr, cmÀ1): 3094 (aromatic
νC H), 2969, 2876 (aliphatic νC H), 1597 (νC N), 1421 (νC C), 839
(νPF6). 1H NMR (400 MHz, DMSO-d6, δ, ppm): 1.08 (d, 6H, J = 6.8 Hz,
p-cymene H16,17), 2.15 (s, 3H, p-cymene H10), 2.75 (m, 1H, p-cymene
H15), 4.44 (s, 2H, Daf-H9), 6.07 (d, 2H, J = 6.1 Hz, p-cymene H13,13′),
6.29 (d, 2H, J = 5.6 Hz, p-cymene H12,12′), 7.79 (dd, 2H, J = 7.6 and
5.4, Daf-H2,7), 8.33 (d, 2H, J = 7.6 Hz, Daf-H1,8), 9.24 (d, 2H,
J = 5.4 Hz, H3,6). 13C NMR (100 MHz, DMSO-d6, δ, ppm): 161.16
(C4a/4b), 151.80 (C3,6), 137.29 (C2,7), 137.15 (C9a/8a), 127.10 (C1,8),
104.02 (C11), 100.38 (C14), 83.24 (C12,12′), 81.72 (C13,13′), 37.80 (C9),
31.07 (C15), 22.18 (C16,17), 18,62 (C10). ESI-MS m/z: 439. Anal. Calcd
for C21H22N2RuClPF6 (%): C, 43.20; H, 3.81; N, 4.80. Found (%): C,
43.03; H, 3.64; N, 4.62.
Complex 1
Yield (89%); m.p. 236–238 °C. FT-IR (KBr, cmÀ1): 3097, 3045
(aromatic νC H), 2972, 2932, 2878 (aliphatic νC H), 1742 (νC O),
1
1584 (νC N), 1423 (νC C), 842 (νPF6). H NMR (400 MHz, DMSO-d6,
Complex 5
δ, ppm): 1.15 (d, 6H, J = 6.8 Hz, p-cymene H16,17), 2.16 (s, 3H,
p-cymene H10), 2.81 (m, 1H, p-cymene H15), 6.11 (d, 2H, J = 6.2 Hz,
p-cymene H13,13′), 6.33 (d, 2H, J = 6.3 Hz, p-cymene H12,12′), 7.90
(dd, 2H, J = 7.4 and 5.5 Hz, Daf-H2,7), 8.39 (d, 2H, J = 7.4, Daf-H1,8),
9.37 (d, 2H, J = 5.5 Hz, Daf-H3,6). 13C NMR (100 MHz, DMSO-d6,
δ, ppm): 185.46 (C9), 164.96 (C4a/4b), 156.73 (C3,6), 135.34
(C1,8), 130.27 (C2,7), 125.72 (C9a/8a), 104.55 (C11), 100.75 (C14),
83.04 (C12,12′), 82.03 (C13,13′), 31.07 (C15), 22.28 (C16,17), 18.61
(C10). ESI-MS m/z: 453. Anal. Calcd for C21H20N2ORuClPF6 (%): C,
42.18; H, 3.38; N, 4.69. Found (%): C, 41.82; H, 3.29; N, 4.56.
Yield (93%); m.p. > 300 °C. FT-IR (KBr, cmÀ1): 3021 (aromatic
νC H), 2965, 2871 (aliphatic νC H), 1596 (νC N), 1419 (νC C), 840
(νPF6). 1H NMR (400 MHz, DMSO-d6, δ, ppm): 1.06 (d, 12H,
J = 6.6 Hz, p-cymene H16,17), 2.12 (s, 6H, p-cymene CH3Ph,
H10), 2.72 (m, 2H, p-cymene H15), 5.78 (s, 2H, Daf-H9), 6.04
(d, 4H, J = 4.8 Hz, p-cymene H13,13′), 6.22 (d, 4H, J = 4.8 Hz,
p-cymene H12,12′), 7.56 (b, 4H, Daf-H2,7), 7.68 (b, 4H, Daf-H1,8),
9.21 (b, 4H, Daf-H3,6). 13C NMR (100 MHz, DMSO-d6, δ, ppm):
160.43 (C4a/4b), 152.94 (C3,6), 137.06 (C8a/9a), 136.79 (C1,8), 127.74
(C2,7), 104.30 (C11), 100.19 (C14), 82.88, 82.52 (C12,12′), 82.34,
81.88 (C13,13′), 49.92 (C9), 31.04 (C15), 22.29 (C16,17), 18.70 (C10).
ESI-MS m/z: 437. Anal. Calcd for C42H42N4Ru2Cl2P2F12 (%): C,
43.27; H, 3.64; N, 4.81. Found (%): C, 43.31; H, 3.58; N, 4.74.
Complex 2
Yield (79%); m.p. 245–247°°C. FT-IR (KBr, cmÀ1): 3556 (νO H), 3050,
3033 (aromatic νC H), 2961, 2922 (aliphatic νC H), 1689 (νC O),
1610 1576, 1447 (νC N and νC C), 1386 (νC N), 847 (νPF6). 1H NMR
(400 MHz, DMSO-d6, δ, ppm): 1.10 (d, 6H, J = 6.9 Hz, p-cymene
Complex 6
H16,17), 2.14 (s, 3H, p-cymene H10), 2.74 (m, 1H, p-cymene H15), 5.90
Yield (86%), m.p. > 300 °C. FT-IR (KBr, cmÀ1): 3094 (aromatic νC H),
2969, 2879 (aliphatic νC H), 1603 (νC N), 1537, 1508 (νC C), 841
(νPF6).[1]HNMR (400 MHz, DMSO-d6, δ, ppm): 1.60 (d, 12H,
J = 5.4 Hz, p-cymene H16,17), 2.20 (s, 6H, p-cymene H10), 2.76–2.86
(m, 2H, p-cymene H15), 6.13 (d, 4H, J = 5.7 Hz, p-cymene H13,13′),
6.36 (d, 4H, J = 6.0 Hz, p-cymene H12,12′), 7.88 (dd, 4H, J = 7.9 and
(d, 2H, J = 4.9 Hz, p-cymene H13,13′), 6.00 (d, 1H, J = 4.9 Hz, Daf-H2),
6.23 (d, 2H, J = 4.8 Hz, p-cymene H12,12′), 7.37 (dd, 1H, J = 7.8 and
4.8 Hz, Daf-H7), 7.55 (d, 1H, J = 5.8 Hz, Daf-H1), 7.92 (d, 1H,
J = 7.8 Hz, Daf-H8), 8.99 (d, 1H, J = 4.8 Hz, Daf-H6). 13C NMR
(100 MHz, DMSO-d6, δ, ppm): 185.30 (C9), 171.08 (C3), 170.19 (C4a),
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Appl. Organometal. Chem. (2016)