Dissertation

|6.2 Synthesis of the Metal Complexes|
solid were removed by filtration through oven dried celite. Remaining product was washed from
the celite with dichloromethane and acetonitrile. Finally the solvent was removed under vacuum
and the crude was redissolved in THF. The pure product was precipitated by slow addition of
diethyl ether. The solid was filtered off and was dried under vacuum. Yield: 103 mg (74.2 µmol,
85%) of a red powder, sensitive to air and moisture.
CH 3 '-bpy
CH 3 -bpy
3'-bpy
5'-bpy N
6'-bpy
3-bpy
N
N
5-bpy
9-ip 10-ip N6-bpy
11-ip
N
CH 2 COD
N
COD
COD
Ru 2+
Rh
N
N 2-ip
Cl
COD
6-ip 4-ip
5-ip
Ar
Ar
Ar
Ru(bbip)Rh
1
H-NMR (400 MHz, CDCl 3 ): δ = 8.62 (dd, 1H (4ip) ,
4
J = 1.0 Hz, 3
J = 8.6 Hz), 8.59 (dd, 1H (11ip) , 4
J =
1.0 Hz, 3 J = 8.6 Hz), 8.53 (d, 1H (3bpy) , 4 J = 1.8Hz),
8.50 (d, 2H (3’bpy, 3”bpy) , 4 J = 1.8Hz), 8.45 (d, 1H (3”’bpy) ,
4
J = 1.8 Hz), 7.98 (dd, 1H (6ip) , 4
J = 1.0 Hz, 3
J =
5.3 Hz), 7.95 (dd, 1H (9ip) , 4 J = 1.0 Hz, 3 J = 5.3 Hz),
7.60 (d, 2H (6,6’bpy) , 3
J = 5.9 Hz), 7.55 (dd, 1H (5ip) ,
3
J = 5.3 Hz, 3
J = 8.7 Hz), 7.57 (dd, 1H (10ip) , 3
J =
5.1 Hz, 3 J = 8.5 Hz), 7.43 (dd, 1H (5bpy) , 4 J = 2.1 Hz, 3 J = 6.0 Hz), 7.41 (dd, 1H (5’bpy) , 4 J = 2.1 Hz,
3
J = 6.0 Hz), 7.35 (m, 11H (Ar+6”bpy) ), 7,232 (d, 1H (6”’bpy) , 3
J = 6.0 Hz), 7.23 (dd, 1H (5”bpy) , 4
J =
1.9 Hz, 3 J = 6.0 Hz), 7.14 (dd, 1H (5”’bpy) , 4 J = 2.0 Hz, 3 J = 6.1 Hz), 7,05 (d, 1H (CH2 ), 2 J = 17.4 Hz),
7,01 (s, 2H (CH2 )), 7,00 (d, 1H (CH2 ), 2 J = 17.4 Hz), 4.99(s, 2H (COD) ), 4.03 (s, 2H (COD) ), 3.41 (m,
2H (COD) ), 2.31 (m, 4H (COD) ), 1.79 (m, 2H (COD) ), 1.41 (s, 9H (CH3 )), 1.41 (s, 9H (CH3 ’)), 1.36 (s,
9H (CH3 ”)) ppm. MS (ESI): m/z = 1567.2 (15%, [{(tbbpy) 2 Ru}(bbip){Rh(COD)Cl} 2 ] 2+ [Cl] - ), 1463.2
(35%, [{(tbbpy) 2 Ru}(bbip){Rh(COD)Cl}⋅{AgCl}] 2+ [Cl] - ), 1319.3 (12%,
[{(tbbpy) 2 Ru}(bbip){Rh(COD)Cl}] 2+ [Cl] - ), 642.3 (100%, [{(tbbpy) 2 Ru}(bbip){Rh(COD)Cl}] 2+ ),
519.4 (45%, [(tbbpy) 2 Ru(bbip)] 2+ ), all with well matching isotopic pattern.
6.2.21 [{Ru(tbbpy) 2 }(µ-bbip){PdCl 2 }]Cl 2 - Ru(bbip)Pd
Under argon atmosphere 100 mg (87.3 µmol) of [Ru(tbbpy) 2 (µ-bbip)AgCl]Cl 2 and 26,7 mg
(87.3 µmol) of [Pd(acetonitrile) 2 Cl 2 ] were dissolved in 20 ml of dry dichloromethane and were
stirred for 16 hours at room temperature (method C3). A colorless precipitate formed after 30 min.
After the reaction time the solid was removed by filtration through oven dried celite. Remaining
product was washed from the celite with dichloromethane and acetonitrile. Finally the solvent was
removed completely under vacuum. The product was obtained as a red powder which decomposes
|232|