Dissertation

|6.2 Synthesis of the Metal Complexes|
CH 3 -bpy
1
H-NMR (CD 3 CN, 400 M Hz): δ = 9.04 (dd, 1H (4/11-ip) , 3 J
CH 3 '-bpy
3'-bpy
5'-bpy N
6'-bpy
3-bpy
N
9-ip 10-ip
N6-bpy
11-ip
Ru 2+
N
5-bpy
N
N
6-ip 4-ip
5-ip
Ru(eip)
CH 2
N
N
2-ip
CH 3
= 8.2 Hz, 4 J = 1.1 Hz), 8.88 (dd, 1H (4/11-ip) , 3 J = 8.6 Hz, 4 J =
1.1 Hz), 8.50 (dd, 1H (3-bpy) , 4 J = 2.0 Hz, 4 J = 2.0 Hz), 8.46
(dd, 1H (3’-bpy) , 4 J = 1.8 Hz, 4 J = 1.8 Hz), 8.34 (s, 1H (2-ip) ), 7.99
(dd, 1H (6/9-ip) , 3 J = 5.4 Hz, 4 J = 1.2 Hz), 7.98 (dd, 1H (6/9-ip) , 3 J
= 5.3 Hz, 4 J = 1.2 Hz), 7.80 (dd, 1H (5/10-ip) , 3 J = 5.4 Hz, 3 J =
8.2 Hz), 7.78 (dd, 1H (5/10-ip) , 3 J = 5.3 Hz, 3 J = 8.4 Hz), 7.69 (d,
1H (6-bpy) , 3 J = 6.1 Hz), 7.67 (d, 1H (6-bpy) , 3 J = 6.1 Hz), 7.47 (dd,
1H (5-bpy) , 3 J = 5.7 Hz, 4 J = 2.7 Hz), 7.46 (dd, 1H (5-bpy) , 3 J = 5.5 Hz, 4 J = 2.4 Hz), 7.42 (dd, 1H (6’-bpy) ,
3
J = 6.0 Hz), 7.41 (dd, 1H (6’-bpy) , 3 J = 6.0 Hz), 7.19 (d, 2H (5’-bpy) , 3 J = 6.0 Hz), 4.77 (q, 2H (CH2 ), 3 J
= 7.2 Hz), 1.65 (t, 3H (CH3 ), 3 J = 7.2 Hz), 1.44 (s, 18H (CH3 -bpy)), 1.35 (s, 18H (CH ′
3 -bpy)) ppm. 13 C-NMR
(CD 3 CN, 100 M Hz): δ = 163.48 (2C (4-bpy) ), 163.31 (2C (4’-bpy) ), 157.89 (2C (2-bpy) ), 157.70 (2C (2’-bpy) ),
151.90 (2C (6-bpy) ), 151.83 (2C (6’-bpy) ), 150.95 (1C (6/9-ip) ), 150.41 (1C (6/9-ip) ), 146.99 (1C (7’/7”-ip) ), 146.73
(1C (7’/7”-ip) ), 146.03 (1C (2-ip) ), 131.20 (1C (4/11-ip) ), 130.59 (1C (4/11-ip) ), 127.52 (1C (3”/11’-ip) ), 127.11 (1C (5/10-ip) ),
126.06 (1C (5/10-ip) ), 125.97 (1C (3”/11’-ip) ), 125.62 (2C (5-bpy) ), 125.42 (2C (5’-bpy) ), 123.05 (2C (3’/11”-ip) ), 122.40
(2C (3-bpy) ), 122.29 (2C (3’-bpy) ), 43.77 (1C (CH2 )), 36.30 (2C (C-bpy) ), 36.19 (2C (C’-bpy) ), 30.54 (6C (CH3 -bpy)),
30.44 (6C (CH3 ’-bpy)), 15.99 (1C (CH3 )) ppm. MS (ESI): m/z = 1031.1 (100%, [M-PF 6 ] + ).
Crystals suitable for X-ray diffraction
were obtained from water/acetone.
Crystal data for Ru(ebip):
[C 51 H 60 N 8 Ru] 2+ [PF 6 ] − 2 × 3 CH 3COCH 3 ,
M r = 1350.31 g /mol, red-brown plate, size
0.05 × 0.05 × 0.03 mm 3 , triclinic, space
group P1 (No. 2), a = 13.429(3), b =
14.934(3), c = 19.146(4) Å, α = 107.11(3),
β = 96.87(3), γ = 96.58(3)°, V =
3407.7(12) Å 3 , T = -90(2)°C, Z = 2, ρ calcd.
= 1.315 g /cm 3 , µ (Mo-Kα) = 3.56 cm -1 , F(000)
= 1400, 20389 reflections in h(-17/17), k(-18/19), l(-23/21) measured in the range 3.96° ≤ Θ ≤ 27.49°,
completeness Φ max = 92.4%, 14481 independent reflections, R int = 0.0396, 9212 reflections with F o >
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