Dissertation

|6.2 Synthesis of the Metal Complexes|
6.2.13 [Ru(tbbpy) 2 (bip)][PF 6 ] 2 - Ru(bip)
Following method C1, 190 mg (268 µmol) of [Ru(tbbpy) 2 Cl 2 ] and 83.2 mg (268 µmol) of bip were
brought to reaction for 90 minutes to yield 154 mg (134 µmol, 95%) of the desired complex as red
powder. The product was recrystallized from an toluene/dichloromethane mixture and could be
purified by column chromatography using dichloromethane/acetone (5:1) as solvent and silicagel
60 as stationary phase. Crystals for suitable for X-ray crystallography were obtained from an
acetonitrile/water/methanol mixture (20:2:1).
CH 3 '-bpy
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(bip)
CH 2
N
N
ph
2-ip
ph
ph
1
H-NMR (CD 3 CN, 400 MHz): δ = 9.080 (dd, 1H (4/11-bip) ,
3
J = 8.2 Hz, 4
J = 1.2 Hz), 8.580 (dd, 1H (11/4-bip) , 3
J =
8.6 Hz, 4 J = 1.2 Hz), 8.508 (d, 1H (3/3’-bpy) , 4 J = 2 Hz), 8.482
(d, 1H (3/3’-bpy) , 4 J = 2 Hz), 8.463 (d, 1H (3’/3-bpy) , 4 J = 2 Hz),
8.463 (s, 1H (2-bip) ), 8.436 (d, 1H (3’/3-bpy) , 4 J = 2 Hz), 8.001
(dd, 1H (6/9) , 3 J = 5.3 Hz, 4 J = 1.3 Hz), 7.923 (dd, 1H (9/6) , 3 J
= 5.3 Hz, 4 J = 1.1 Hz), 7.790 (dd, 1H (5/10) , 3 J = 8.3 Hz, 3 J
= 5.3 Hz), 7.66 (dd, 2H (5/5’-bpy) , 3 J = 5.9 Hz, 4 J = 7.1 Hz),
7.58 (dd, 1H (10/5) , 3 J = 8.5 Hz, 3 J = 5.3 Hz), 7.452 (dd, 1H (5’/5-bpy) , 3 J = 5.4 Hz, 4 J = 2.0 Hz), 7.438
(dd, 1H (5’/5-bpy) , 3 J = 5.4 Hz, 4 J = 2.0 Hz), 7.394 (d, 1H (6/6’-bpy) , 3 J = 6.2 Hz), 7.389 (d, 1H (6/6’-bpy) , 3 J =
6.2 Hz), 7.33 (m, 3H (Ar)) , 7.21 (m, 2H (Ar) ), 7.184 (d, 1H (6’/6-bpy) , 3 J = 6.2 Hz), 7.178 (d, 1H (6’/6-bpy) , 3 J =
6.2 Hz), 5.984 (s, 2H (CH2 )), 1.44 (s, 9H (CH3 )), 1.43 (s, 9H (CH3 )) 1.35 (s, 9H (CH3 )), 1.34 (s, 9H (CH3 )) ppm;
13
C-NMR (CD 3 CN, 400 MHz): δ = 163.55 (2C (4/4’-bpy) ), 163.42 (2C (4’/4-bpy) ), 157.97 (2C (2/2’-bpy) ),
157.78 (2C (2’/2-bpy) ), 152.11 (2C (5/5’-bpy) ), 151.92 (2C (2’/2-bpy) ), 151.29 (1C (6/9-bip) ), 150.75 (1C (9/6-bip) ),
147.48 (1C (2-bip) ), 147.22 (1C (8’/8”-bip) ), 147.04 (1C (8”/8’-bip) ), 139.01 (1C (3’/11”-bip) ), 136.47 (1C ( t C-ph)), 131.27
(1C (4/11-bip) ), 130.60 (1C (11/4-bip) ), 130.20 (2C (ph) ), 129.27 (1C (ph) ), 127.58 (1C (11”/3’-bip) ), 127.37 (2C (ph) ),
127.26 (1C (5/10-bip) ), 126.29 (1C (10/5-bip) ), 125.59 (2C (6/6’-bpy) ), 125.40 (2C (6’/6-bpy) ), 122.80 (1C (3”/11’-bip) ),
122.46 (2C (3/3’-bpy) ), 122.40 (1C (3’/3-bpy) ), 122.12 (1C (11’/3”-bip) ), 51.71 (1C (CH2 -bip)), 36.33 (2C (tC/tC’-bpy) ),
36.26 (2C (tC’/tC-bpy) ), 30.49 (6C (CH3 /CH 3 ’-bpy)), 30.41 (6C (CH3 ’/CH 3 -bpy)) ppm; MS (ESI) m/z = 474.2
(40%, [M-2PF 6 ] 2+ ), 848.2 (5%, [M-2PF 6 ] + ), 1093.2 (100%, [M-PF 6 ] + );
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