Dissertation

|6.2 Synthesis of the Metal Complexes|
137.34 (2C (2,3,5,6-Durol) ), 131.49 (2C (4-ip) ), 130.74 (2C (11-ip) ), 129.38 (2C (1,4-Durol) ), 127.50 (2C (3’) ), 127.14
(2C (5) ), 126.96 (2C (11”) ), 126.74 (2C (10) ), 124.82 (4C (5-bpy) ), 124.58 (4C (5’-bpy) ), 121.75 (8C (6/6’-bpy) ),
121.66 (2C (3”-ip) ), 121.03 (2C (11’-ip) ), 51.00 (2C (CH2 -Ar)), 46.42 (2C (CH2 -Al)), 35.48 (2C (C-tBu) ), 35.37
(2C (C-tBu) ), 29.58 (12C (CH3 - t Bu)), 29.49 (12C (CH3 - t Bu)), 16.19 (4C (CH3 -Ar)), 14.33 (2C (CH3 -Al)) ppm. MS
(ESI): m/z = 1110.2 (10%, [M - 2 PF 6 ] 2+ ) 1031.1 (100%, [Ru(eip)+ PF 6 ] + ).
6.2.25 [{(tbbpy) 2 Ru} 2 (µ-edip){AgCl} 2 ]Cl 4 - Ru 2 (edip)Ag 2
According to method C2, 200 mg (93 µmol) of the chloride salt of Ru 2 (edip), 25.0 mg (220 µmol)
of silver(I) oxide and 2 g of dry molecular sieves were suspended in 20 ml of dry dichloromethane
under argon atmosphere. This solution was stirred for 16 hours at room temperature. After
the reaction time, the remaining solids were removed by filtration through oven dried celite.
Remaining product was washed from the celite with dichloromethane and acetonitrile. The pure
product is obtained after removal of the solvent under reduced pressure. Yield: 190 mg (80 µmol,
86%) of a red powder which is sensitive to air and moisture.
CH 3 -bpy
1
H-NMR (CD 3 CN,
N
N
N
9-ip 10-ip CH
11-ip CH 3 2
N
N
N
Ru 2+ Ag
Cl
N
N
Cl
Ag
N
N
6-ip 4-ip
5-ip
Ar
Ru 2 (edip)Ag 2
5-bpy
6-bpy
N
N
N
Ru 2+
N
3-bpy
3'-bpy
N 5'-bpy
6'-bpy
N
CH 3 '-bpy
400 MHz): δ= 9.50
(d, 2H (C) ,
3
J = 8.4Hz), 9.03 (d,
2H (C’) , 3 J = 8.6Hz),
8.58 (d, 2H (3-bpy) , 4 J
= 1.8Hz),
8.58 (d, 2H (3’-bpy) , 4 J
= 1.8Hz), 8.54 (d, 2H (3”-bpy) , 4 J = 2.0Hz), 8.54 (d, 2H (3”’-bpy) , 4 J = 1.8Hz), 8.20 (dd, 2H (A) , 3 J = 5.3Hz,
4
J = 0.7Hz), 8.18 (dd, 2H (A’) , 3 J = 5.4Hz, 4 J = 0.8Hz), 7.91 (dd, 2H (B) , 3 J = 8.8Hz, 3 J = 4.8Hz), 7.90
(dd, 2H (B’) , 3 J = 8.7Hz, 3 J = 5.1Hz), 7.72 (d, 2H (6-bpy) , 3 J = 6.1Hz), 7.70 (d, 2H (6’-bpy) , 3 J = 6.1Hz),
7.49 (m, 2H (5,5’,6”-bpy) ), 7.45 (d, 6H (6”’-bpy) , 3 J = 6.1Hz), 7.26 (m, 4H (5”,5”’-bpy) ), 6.10 (d, 2H (CH2 -Ar), 2 J =
13.1Hz), 6.05 (d, 2H (CH2 -Ar), 2 J = 14.3Hz), 5.06 (q, 4H (CH2 -Al), 3 J = 6.8Hz), 2.30 (dd, 12H (CH3 -Ar), J
= 23.9Hz, J = 6.2Hz), 1.70 (t, 6H (CH3 -Al), 3 J = 7.1Hz), 1.46 (s, 36H (tBu) ), 1.38 (s, 36H (tBu) ) ppm. MS
(ESI): m/z = 1143.8 (25%, [M – 2 Cl] 2+ ), 751.1 (50%, [M – 3 Cl] 3+ ), 715.1 (50%, [M – 3 Cl – Ag] 3+ ),
554.7 (100%, [M – 3 Cl] 4+ ).
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