Dissertation

|6.2 Synthesis of the Metal Complexes|
6.2.3 Transmetallation of [Ag(NHC)X]-type complexes - method C3
Under argon atmosphere one equivalent (e.g. 100 µmol) of [Ru(tbbpy) 2 (µ-bbip)AgCl]Cl 2 and one
equivalent of the starting complex for the transmetallation reaction were dissolved in 20 ml of dry
dichloromethane. After stirring for 2-16 hours at room temperature a colorless precipitate was
formed. The solid was removed by filtration through oven dried celite after the reaction time. The
celite was washed with dry dichloromethane or acetonitrile to obtain remaining product. Finally
the solvent was removed completely under vacuum. The product was obtained as a red powder
which decomposes under air. Yield: (∼95%).
6.2.4 [Ru(tbbpy) 2 (phen-5-Br)][PF 6 ] 2 - Ru(phenBr)
According to method C1, 664 mg (936 µmol) of [Ru(tbbpy) 2 Cl 2 ] and 355 mg (936 µmol) of
phenBr were reacted in the microwave for 90 minutes in 125 ml of ethanol/water. After cooling,
ethanol was removed and precipitated impurities were filtered off. Then 916 mg (5.62 mmol)
NH 4 PF 6 were added and the formed precipitate was filtered collected and was washed with water.
Purification was achieved by recrystallization from acetone/water by slow evaporation. This
yielded also crystals suitable for X-ray diffraction. After removal of water the pure Ru(phenBr)
was obtained as red powder. The yield is 1.07 g (898 µmol, 96%).
CH 3 -bpy
1
H-NMR (CD 3 CN, 400 MHz): δ = 8.79 (dd, 1H (4) , 3 J = 8.2 Hz,
CH 3 '-bpy 3-bpy
5-bpy
3'-bpy
8
6-bpy
N 9 7
5'-bpy N
N
6
6'-bpy
Ru 2+
N
N
Br
N 2 4
3
Ru(phenBr)
4
J = 1.2 Hz), 8.61 (s, 1H (6) ), 8.51 (dd, 1H (7) , 3 J = 8.2 Hz, 4 J =
1.2 Hz), 8.50 (m, 2H (3-bpy) ), 8.46 (m, 2H (3’-bpy) ), 8.11 (dd, 1H (2) , 3 J
= 4.8 Hz, 4 J = 0.8 Hz), 8.07 (dd, 1H (9) , 3 J = 4.6 Hz, 4 J = 1.2 Hz),
7.83 (dd, 1H (3) , 3 J = 8.4 Hz, 3 J = 5.2 Hz), 7.67 (dd, 2H (6-bpy) ,
3
J = 6.0 Hz, J = 3.0 Hz), 7.45 (ddd, 2H (5-bpy) , 4 J = 1.6 Hz, 4 J
= 1.8 Hz, 3 J = 5.8 Hz), 7.38 (dd, 2H (6’-bpy) , 3 J = 5.8 Hz, 3 J =
4.2 Hz), 7.21 (m, 2H (5’-bpy)) , 1.43 (d, 18H (t-Bu’) , J = 1.0 Hz), 1.35
(s, 18H (t-Bu) ) ppm. 13 C-NMR (CD 3 CN, 100 MHz): δ = 163,73 (2C (4-bpy) ), 163,59 (2C (4’-bpy) ), 158.05
(2C (2-bpy) ), 157.76 (2C (2’-bpy) ), 154.00 (1C (2) ), 153.67 (1C (9) ), 152.28 (2C (6’-bpy) ), 152.06 (2C (6-bpy) ), 149.73
(1C (10”) ), 148.45 (1C (10’) ), 137.05 (1C (4) ), 136.52 (1C (7) ), 132.08 (1C (6) ), 131.89 (1C (6’) ), 131.44 (1C (4’) ),
127.67 (1C (3) ), 127.61 (1C (8) ), 125.64 (2C (5-bpy) ), 125.45 (2C (5’-bpy) ), 122.72 (1C (5) ), 122.53 (2C (3-bpy) ),
122.44 (C (3’-bpy) ), 36.36 (2C (7’-bpy) ), 36.27 (2C (7-bpy) ), 30.52 (3C (8’-bpy) ), 30.44 (3C (8-bpy) ) ppm.
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