Dissertation

|6.2 Synthesis of the Metal Complexes|
reflections, R int = 0.0364, 8038 reflections with F o > 4σ(F o ), 659 parameters, 0 restraints, R obs.
= 0.0545, wR 2 obs. = 0.1422, R all = 0.0935, wR 2 all
= 0.1618, GOOF = 1.032, largest difference peak and
hole: 1.730 / -0.919 e /Å 3 . The data file TT3727 includes the full crystallographic data and can be
obtained from Dr. Helmar Görls (IAAC, FSU-Jena).
6.2.8 [Ru(phenBr 2 ) 3 ][PF 6 ] 2 - Ru(phenBr 2 ) 3
For this reaction 131 mg (468µmol) of [Ru(COD)Cl 2 ] n and 474 mg (1.40 mmol) of phenBr 2 were
heated in a mixture of ethanol/water over night at reflux and afterwards for two hours in the
microwave (150 W). After removal of the solvent and the in water insoluble side products, NH 4 PF 6
was added. Purification was achieved using column chromatography in acetonitrile/water.
Recrystallization from acetonitrile gave the desired product in high purity. Yield: 17%, 109 mg,
31.2 µmol. 1 H-NMR (CDCl 3 , 400 MHz): δ = 8.876 (dd, 6H (4/7) , 3 J = 8.2 Hz, 4 J = 1.2 Hz), 8.526 (dd,
1H (2/9) , 3 J = 5.6 Hz, 4 J = 1.2 Hz), 8.034 (dd, 1H (3/8) , 3 J = 8.8 Hz, 3 J = 5.2 Hz) ppm. 13 C-NMR (CDCl 3 ,
100 MHz): δ = 155.14 (6C (4/7) ), 148.49 (6C (10’/10”) ), 138.80 (6C (2/9) ), 131.99 (6C (4’/6’) ), 128.21 (6C (3/7) ),
127.21 (6C (5/6) ) ppm. MS: (ESI) m/z = 1206.2 (100%, [M-PF 6 ] + ).
Crystals suitable for X-ray diffraction were
obtained from acetonitrile/water. Crystal data
for Ru(phenBr 2 ) 3 : [C 36 H 18 N 6 Br 6 Ru] 2+ [PF 6 ] − 2
× 1.5 CH 3 CN, M r = 1394.13 g /mol, red-brown
cuboid, size 0.06 × 0.05 × 0.05 mm 3 , hexagonal,
space group P31c (No. 163), a = 18.4621(4), b
= 18.4621(4), c = 21.0210(5) Å, α = 90.000, β
= 90.000, γ = 120.000°, V = 6205.1(2) Å 3 , T
= -90°C, Z = 4, ρ calcd. = 1.492 g /cm 3 , µ (Mo-Kα) =
42.11 cm -1 , F(000) = 2666, 41120 reflections in
h(-21/23), k(-23/21), l(-27/26) measured in the
range 3.20° ≤ Θ ≤ 27.50°, completeness Φ max
= 99.7%, 4761 independent reflections, R int = 0.0757, 3113 reflections with F o > 4σ(F o ), 181
parameters, 0 restraints, R obs. = 0.0929, wR 2 obs.
= 0.2732, R all = 0.1334, wR 2 all
= 0.3151, GOOF =
1.052, largest difference peak and hole: 2.812/-1.127 e /Å 3 . The data file TT3691 includes the full
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