Dissertation

|6.1 Synthesis of the Organic Ligands|
Crystals suitable for X-ray diffraction were obtained
from diluted trifuoroacetic acid. Crystal data for ip:
[C 13 H 8 N 4 ] + × [CF 3 COO] - , M r = 334.26 g /mol, colorless
cuboid, size 0.05 × 0.05 × 0.04 mm 3 , monoclinic, space
group P1 1 /n (No. 14), a = 13.6042(8), b = 6.9560(6), c =
16.6210(12) Å, α = 90.000, β = 111.634(4), γ = 90.000°, V
= 1462.06(19) Å 3 , T = -90(2)°C, Z = 2, ρ calcd. = 1.519 g /cm 3 ,
µ (Mo-Kα) = 1.3 cm -1 , F(000) = 680, 9652 reflections in h(-
17/17), k(-7/9), l(-21/21) measured in the range 2.64° ≤ Θ
≤ 27.45°, completeness Φ max = 99.3%, 3308 independent
reflections, R int = 0.0508, 2023 reflections with F o >
4σ(F o ), 248 parameters, 0 restraints, R obs. = 0.0669, wR 2 obs.
= 0.1695, R all = 0.1152, wR 2 all = 0.1971,
GOOF = 1.017, largest difference peak and hole: 0.403/-0.341 e /Å 3 . The data file TT3762 includes
the full crystallographic data and can be obtained from Dr. Helmar Görls (IAAC, FSU-Jena).
In the molecular structure of ip false-ordered fluorine atoms are omitted for clarity. Ellipsoids are
drawn at 70% probability. Selected bond length (Å) and angels (°):
6.1.9 1-Benzyl-1H-imidazo[4,5-f][1,10]phenanthrolin - bip
Following the general procedure according to method L2, 2.0 g (9.1 mmol) of ip were
deprotonated with 523 mg (13.1 mmol) of sodium hydride (60% in paraffin) under argon
atmosphere in 10 ml of dry DMF. Then 1.30 ml (10.9 mmol) of benzyl bromide were added to the
stirred sodium imidazolide solution. After the reaction time of three hours at room temperature
the solvent was removed completely under vacuum and the residue was redissolved in chloroform
and washed with water. The combined organic phases were dried over Na 2 SO 4 . Purification was
achieved by column chromatography using chloroform and silica gel 60 as phase system. Yield:
1.9 g (6.1 mmol, 74%) of a colorless solid.
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