Dissertation

|6.2 Synthesis of the Metal Complexes|
CH 3 -bpy
1
H-NMR (CD 3 CN, 400 MHz): δ = 8.92 (d, 2H (ip 4/11) , 3
J =
CH 3 '-bpy
3'-bpy
5'-bpy N
6'-bpy
3-bpy
N
9-ip 10-ip
N6-bpy
11-ip
Ru 2+
N
5-bpy
N
N
6-ip 4-ip
5-ip
Ru(ip)
H
N
N
2-ip
8.1 Hz), 8.52 (d, 2H (bpy 3/3’) , 4
J = 1.9 Hz), 8.47 (d, 2H (bpy 3’/3) ,
4
J = 1.9 Hz), 8.42 (s, 1H (ip2) ), 7.99 (dd, 2H (ip6/9) , 4 J = 0.9 Hz,
3
J = 5.2 Hz), 7.78 (dd, 2H (ip 5/10) , 3
J = 5.3 Hz, 3
J = 8.3 Hz),
7.69 (d, 2H (bpy 6/6’) , 3
J = 6.0 Hz), 7.46 (dd, 2H (bpy 5/5’) , 4
J =
2.0 Hz, 3 J = 6.0 Hz), 7.44 (d, 2H (bpy 6’/6) , 3 J = 6.1 Hz), 7.19 (dd,
2H (bpy 5’/5) , 4
J = 2.0 Hz, 3
J = 6.1 Hz), 1.45 (s, 18H (tBu) ), 1.35
(s, 18H (tBu’) ) ppm. 13 C-NMR (CD 3 CN, 100 MHz): δ = 163.51
(2C (4/4’-bpy) ), 163.33 (2C (4’/4-bpy) ), 157.99 (2C (2/2’-bpy) ), 157.75 (2C (2’/2-bpy) ), 152.07 (2C (6/6’-bpy) ), 151.93
(2C (6’/6-bpy) ), 150.90 (2C (6/9-ip) ), 146.97 (2C (7’/7”-ip) ), 143.32 (1C (2-ip) ), 131.15 (2C (4/11-ip) ), 126.86
(2C (5/10-ip) ), 125.53 (2C (5/5’-bpy) ), 125.37 (2C (5’/5-bpy) ), 122.40 (2C (3/3’-bpy) ), 122.31 (2C (3’/3-bpy) ), 36.29
(2C (tC-bpy) ), 36.18 (2C (tC’-bpy) ), 30.47 (6C (-CH3-bpy) ), 30.37 (6C (-CH3’-bpy) ) ppm. C (3’/11”) and C (3”/11’) were
not found. MS: (ESI) m/z = 429.1 (100%, [M-2PF6 6 ] 2+ ), 856.2 (65%, [M-2PF 6 -H] + ), 1003.1 (40%,
[M-PF 6 ] + ).
Crystals suitable for X-ray diffraction were
obtained from acetone/ethanol/water. Crystal
data for Ru(ip): [C 49 H 56 N 8 Ru] 2+ [PF 6 ] − 2
× 2.5 C 2 H 5 OH, M r = 1256.18 g /mol, red crystal,
size 0.05 × 0.05 × 0.04 mm 3 ,
orthorhombic,
space group P2 1 /n (No. 29), a = 40.0363(6),
b = 12.1313(3), c = 12.4471(3) Å, α = 90.00, β
= 90.00, γ = 90.00°, V = 6045.5(2) Å 3 , T =
183(2) K, Z = 4, ρ calcd. = 1.380 g /cm 3 , µ (Mo-Kα) =
0.395 cm -1 , F(000) = 2596, 32336 reflections in
h(-51/50), k(-12/15), l(-16/16) measured in the
range 2.64° ≤ Θ ≤ 27.48°, completeness Φ max = 99.7%, 13558 independent reflections, R int = 0.0512,
13558 reflections with F o > 4σ(F o ), 716 parameters, 1 restraint, R obs. = 0.0633, wR 2 obs. = 0.1658, R all
= 0.0934, wR 2 all
= 0.1837, GOOF = 1.025, absolute structure parameter: 0.02(4); largest difference
peak and hole: 1.229/-0.554 e /Å 3 . The data file FO3797 includes the full crystallographic data and
can be obtained from Dr. Helmar Görls (IAAC, FSU-Jena).
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