Dissertation

|6.1 Synthesis of the Organic Ligands|
0.0583, wR 2 all = 0.1080, GOOF = 1.052, largest difference peak and hole: 0.914/-0.486 e /Å 3 . The data
file TT3588 includes the full crystallographic data and can be obtained from Dr. Helmar Görls
(IAAC, FSU-Jena).
6.1.6 5,6-Dibromo-2,9-dimethyl-1,10-phenanthroline - phenMe 2 Br 2
The title compound was prepared by the application of method L1. After dissolving 1.0 g
(4.9 mmol) of 2,9-dimethyl-1,10-phenanthroline in 30 ml of fuming sulfuric acid (65%) under
cooling 0.38 ml (7.3 mmol) bromine were added. The emulsion was stirred over night at room
temperature and was poured on 45 ml of ice after the reaction time. The mixture was neutralized
with ammonia (pH 7) and the formed precipitate was extracted with chloroform. Removal of the
solvent yielded the crude product. For the purification, recrystallization of the crude product form
ethanol, ether, methylenchlorid and other solvents did not succeed. In all cases a mixture of the
5,6-dibromo- (phenMe 2 Br 2 ) and the 3,5,6-tribromocompound (phenMe 2 Br 3 ) was obtained.
3
1
CH 3
H-NMR (CDCl 3 , 400 MHz): δ = 8.43 (d, 2H (4/7) , 3 J = 8.6 Hz), 7.41
4
N
N
Br
Br
CH 3
7
8 phenMe 2 Br 2
(d, 2H (3/8) , 3 J = 8.6 Hz), 2.83 (s, 6H (CH3) ) ppm.
13
C-NMR (CDCl 3 ,
100 MHz): δ = 150.92 (2C (2/9) ), 145.09 (2C (10’/10”) ), 137.56 (2C (4’/6’/9) ),
128.74 (2C (4/7) ), 125.27 (2C (5/6) ), 124.60 (2C (3/8) ) 25.60 (2C (CH3) ) ppm.
MS (DEI): m /z = 338 (100%, M + )
Crystals suitable for X-ray diffraction were obtained from chloroform. Crystal data for
phenMe 2 Br 2 /phenMe 2 Br 3 : C 14 H 10 N 2 Br 2 × 2 CHCl 3 and C 13 H 10 N 2 Br 3 × 2 CHCl 3 , M r = 610.32 g /mol,
colorless cuboid, size 0.05 × 0.05 × 0.05 mm 3 , monoclinic, space group P2 1 /c (No. 14), a =
|201|