Dissertation

|6.1 Synthesis of the Organic Ligands|
9
8 N
7 N
6
10
5
11
4
CH 2
Ar
1
H-NMR (CDCl 3 , 400 MHz): δ = 9.168 (dd, 2H (6,9) , 3 J = 4.6 Hz, 4 J =
1.6 Hz), 9.039 (dd, 2H (9,6) , 3 J = 4.6 Hz, 4 J = 1.6 Hz), 8.999 (dd, 2H (4,11) ,
N 1
2
N
3
bip
Ar
Ar
3
J = 8.2 Hz, 4 J = 1.6 Hz), 8.191 (dd, 2H (11,4) , 3 J = 8.2 Hz, 4 J = 1.6 Hz),
8.020 (s, 1H (2)) , 7.729 (dd, 2H (5,10) , 3 J = 8.2 Hz, 3 J = 4.4 Hz), 7.413 (dd,
2H (5,10) , 3 J = 8.2 Hz, 3 J = 4.4 Hz), 7.3 (m, 3H (Ar) ), 7.1 (m, 2H (Ar) ), 7.3 (m,
3H (Ar) ), 5.794 (s, 2H (-CH2) ) ppm. 13 C-NMR (CDCl 3 , 400 MHz): δ = 149.00 (1C (6,9) ), 148.06 (1C (9,6) ),
144.68 (1C (3”,11’) ), 144.15 (1C (11’,3”) ), 143.54 (1C (2) ), 137.67 (1C (3’,11”) ), 134.99 (1C (C1-Ar) ), 130.48 (1C (4,11) ),
129.41 (2C (Ar) ), 128.74 (1C (C4-Ar) ), 128.58 (1C (11,4) ), 126.00 (2C (Ar) ), 124.38 (1C (11”,3’) ), 124.35 (1C (7’,7”) ),
123.68 (1C (5,10) ), 122.59 (1C (10,5) ), 119.58 (1C (7”,7’) ), 51.29 (1C (CH2 )) ppm.
Crystals suitable for X-ray diffraction were obtained
from methanol/water. Crystal data for bip: C 20 H 14 N 4
× 1.5 H 2 O, Mr = 337.38 gmol -1 , colorless cuboid, size
0.06 × 0.04 × 0.04 mm 3 , triclinic, space group P1 (No. 2),
a = 11.2481(3), b = 12.1858(5), c = 12.4532(6) Å, α =
79.993(2), β = 86.406(2), γ = 85.159(2)°, V = 1672.95(11)
Å 3 , T = -90(2)°C, Z = 4, ρ calcd. = 1.339 gcm -3 , µ (Mo-
Kα) = 0.88 cm -1 , F(000) = 708, 11572 reflections in h(-
14/14), k(-15/14), l(-16/15) measured in the range 3.18° ≤
Θ ≤ 27.48°, completeness Φ max = 99.2%, 7621 independent
reflections, R int = 0.0322, 5013 reflections with F o > 4σ(F o ),
460 parameters, 0 restraints, R obs. = 0.0558, wR 2 obs. = 0.1143, R all = 0.1012, wR 2 all
= .01331, GOOF =
1.006, largest difference peak and hole: 0.256 / -0.326 eÅ -3 . The data file TT3947 includes the
full crystallographic data and can be obtained from Dr. Helmar Görls (IAAC, FSU-Jena). In
the ORTEP representation of the molecular structure of bip solvent molecules were omitted for
clarity. Ellipsoids were drawn at 70% probability level.
6.1.10 1,3-Dibenzyl-1H-imidazo[4,5-f][1,10]phenanthrolinium bromide - bbip
As described in method L3, 2.00 g (6.44 mmol) of bip were dissolved in 10 ml of benzyl bromide.
The solution was stirred at 120°C for one hour, forming a viscous yellow precipitate. Then 5 ml of
DMF were added to the stirred solution. After two more hours at 120°C a light yellow precipitate
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