Dissertation

|6.2 Synthesis of the Metal Complexes|
6.2.16 Attempted Preparation of [(bbip)AgBr] n - (bbip)Ag
For the complexation reaction 100 mg of imidazolium bromide bbip and one equivalent of Ag 2 O
were suspended under inert conditions in dry dichloromethane according to method C2. Then
the mixture was stirred for 7 days. Due to the general insolubility of both compounds a no visible
change of the reaction mixture during this time. After this time, the reaction mixture was filtered
through celite under inert conditions because of the expected higher solubility of the neutral
complex compared to the ionic compounds. Removal of the solvent from the colorless solution
gave only a thin film of precipitated white solid in very low yields (< 1%). By dissolution of the
precipitate in dry chloroform-d under inert conditions it was possible to obtain a weak 1 H-NMRspectrum.
10-ip
9-ip 11-ip CH 2 Ar
N N
Ag Br
N N
4-ip
Ar
6-ip
CH 2
5-ip
1
H-NMR (CDCl 3 , 400 MHz): δ = 9.07 (dd, 2H (6/9) , 3 J = 4.3 Hz, 4 J =
1.3 Hz), 8.40 (dd, 2H (4/11) , 3 J = 8.5 Hz, 4 J = 1.3 Hz), 7.48 (dd, 2H (5/10) ,
3
J = 8.5 Hz, 3 J = 4.3 Hz), 7.22 (m, 6H (Ar) ), 7.05 (m, 4H (Ar) ), 6.21 (s,
4H (CH2 )) ppm. Due to the small amount of the obtained product, no
other analysis method could be used.
6.2.17 [{(tbbpy) 2 Ru}(µ-bbip){AgCl}]Cl 2 - Ru(bbip)Ag
According to method C2, 200 mg (175 µmol) of [Ru(tbbpy) 2 (bbip)]Cl 3 , 40.0 mg (175 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 or acetonitrile. The pure
product is obtained after removal of the solvent under reduced pressure. Yield: 197 mg (157.5 µmol,
90%) of a red powder sensitive to air and moisture.
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