Dissertation

|6.2 Synthesis of the Metal Complexes|
Crystals suitable for X-ray diffraction were
obtained from dichloromethane/chloroform.
Crystal data for Ru(bbip): [C 63 H 69 N 8 Ru] 3+ ,
3[PF 6 ] - × 5 CHCl 3 , Mr = 2071.08 g/mol, redbrown
cuboid, size 0.05 × 0.05 × 0.04 mm 3 ,
triclinic, space group P1 (No. 2), a = 13.0496(5),
b = 17.8884(6), c = 20.1331(7) Å, α = 105.144(2),
β = 101.312(2), γ = 101.134(2)°, V = 4297.7(3)
Å 3 , T = -140°C, Z = 2, ρ calcd. = 1.600 gcm -3 ,
µ (Mo-Kα) = 7.89 cm -1 , F(000) = 2088, 29924
reflections in h(-16/15), k(-23/22), l(-26/26) measured in the range 2.86° ≤ Θ ≤ 27.45°, completeness
Θ max = 98%, 19232 independent reflections, R int = 0.0486, 12542 reflections with F o > 4σ(F o ), 1029
parameters, 0 restraints, R obs. = 0.0766, wR 2 obs. = 0.1813, R all = 0.1262, wR 2 all = 0.2124, GOOF =
1.026, largest difference peak and hole: 2.712 / -1.715 e Å -3 . The Cambridge Crystallographic Data
Centre file CCDC-765499 includes the full crystallographic data. In the molecular structure of
Ru(bbip). Hydrogen atoms (except H13a), solvent molecules and anions are omitted for clarity.
Ellipsoids are drawn at 70% probability.
6.2.15 [Ru(tbbpy) 2 (bbip)]Cl 3
For the counter ion exchange 425 mg (1.53 mmol) of NBu 4 Cl were
dissolved in 20 ml of acetone/ethyl acetate (1:1/v:v). After this a solution of 250 mg (170 µmol)
of [Ru(tbbpy) 2 (bbip)][PF 6 ] 3 dissolved in 10 ml of acetone/ethyl acetate (1:1/v:v) was slowly added
to the stirred chloride salt solution. The resulting suspension was stirred for 30 min. Thereafter,
the precipitate was filtered off and washed with 10 ml of acetone/ethyl acetate (1:1/v:v) and twice
with 20 ml of ethyl acetate. After drying under vacuum, 192 mg (99%) of the desired product were
obtained. No changes in the NMR spectra were detected with respect to the hexafluorophosphate
salt of Ru(bbip).
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