Dissertation

|6.2 Synthesis of the Metal Complexes|
6.2.6 [Ru(phenBr 2 ) 2 Cl 2 ] - Ru(phenBr 2 )Cl 2
For this reaction, 280 mg (1.00 mmol) of [Ru(COD)Cl 2 ] n and 676 mg (2.00 mmol) of phenBr 2
were suspended in 50 ml of dry DMF and heated for two hours at 150 W in the microwave.
After cooling, the solvent was removed. The remaining solid was dissolved in a small amount
of chloroform heated to reflux very short. Addition of ethanol and recrystallization in the cold
yielded a black precipitate. Removal of the sideproduct Ru(phenBr 2 ) 3 was be achieved via
extraction of the methylene chloride solution with water and by column chromatography with
acetone/DMF. After removal of the solvent 400 mg (470 µmol) of a black and almost insoluble
powder were obtained (Yield = 47%). 1 H-NMR (CD 2 Cl 2 , 400 MHz): δ = 10.550 (d, 2H (2/9) , 3 J =
4.2 Hz), 9.696 (d, 2H (2/9) , 3 J = 5.2 Hz), 8.837 (d, 4H (4/7) , 3 J = 8.4 Hz), 8.124 (dd, 2H (2/9) , 3 J = 4.2 Hz,
3
J = 8.4 Hz), 7.887 (dd, 2H (2/9) , 3 J = 5.2 Hz, 3 J = 8.4 Hz) ppm.
Crystals suitable for X-ray diffraction were
obtained from dichloromethane. Crystal data for Ru(phenBr 2 )Cl 2 :
[C 24 H 12 N 4 Cl 2 Br 4 Ru] × 3 CH 2 Cl 2 , M r = 1101.76 g /mol, black crystal,
size 0.06 × 0.06 × 0.03 mm 3 , monoclinic, space group C2/c (No. 15),
a = 18.1042(8), b = 16.7210(13), c = 14.0302(9) Å, α = 90.000, β =
125.740(3), γ = 90.000°, V = 3447.4(4) Å 3 , T = -90°C, Z = 4, ρ calcd.
= 2.123 g /cm 3 , µ (Mo-Kα) = 57.39 cm -1 , F(000) = 2108, 11467 reflections
in h(-23/22), k(-21/21), l(-14/18) measured in the range 1.93° ≤ Θ ≤
27.46°, completeness Φ max = 99.5%, 3929 independent reflections,
R int = 0.0634, 2688 reflections with F o > 4σ(F o ), 200 parameters, 0
restraints, R obs. = 0.0468, wR 2 obs. = 0.1075, R all = 0.0834, wR 2 all = 0.1232,
GOOF = 1.040, largest difference peak and hole: 0.981/-0.738 e /Å 3 .
The data file TT3609 includes the full crystallographic data and can be obtained from Dr. Helmar
Görls (IAAC, FSU-Jena).
6.2.7 [Ru(phenBr 2 ) 2 (tbbpy)][PF 6 ] 2 - Ru(phenBr 2 ) 2
Following method C1, 105 mg (124 µmol) of Ru(phenBr 2 ) 2 Cl 2 and 33,2 mg (124 µmol) of tbbpy
were reacted in the microwave for 180 minutes in 100 ml of ethanol/water. After cooling,
ethanol was removed and dark precipitated impurities were filtered off. Then, 121 mg (720 µmol)
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