1810
J. Niemeyer et al. / Journal of Organometallic Chemistry 695 (2010) 1801e1812
4.90 (sept, 3J ¼ 6.1 Hz, 1H, CH1), 4.59 (m, 1H, H-6A), 4.50 (sept,
3J ¼ 6.1Hz, 1H, CH2), 4.31 (ddd, 3J ¼ 2.6 Hz, 4J ¼ 1.4 Hz, 4J ¼ 0.7 Hz,
1H, H-3B), 4.29 (dd, 3J ¼ 2.8 Hz, 4J ¼ 1.3 Hz, 1H, H-5A), 4.24 (ddd,
3J ¼ 2.6 Hz, 4J ¼ 1.3 Hz, 4J ¼ 0.6 Hz, 1H, H-3A), 4.22 (s, 5H, Cp1), 4.20
(dd, 3J ¼ 2.8 Hz, 4J ¼ 1.4 Hz, 1H, H-5B), 4.08 (dd, 3J ¼ 2.8 Hz,
3J ¼ 2.6 Hz, 1H, H-4B), 4.07 (dd, 3J ¼ 2.8 Hz, 3J ¼ 2.6 Hz, 1H, H-4A),
parameters, R¼ 0.089,wR2 ¼ 0.260,Flackparameterꢁ0.010(13), max.
ꢀꢁ3
(min.) residual electron density 0.57 (ꢁ0.37) e A , hydrogen atoms
calculated and refined as riding atoms, due to crystal shape and
disordered solvent molecules the quality of the analysis is poor. CCDC
762154.
3.95 (s, 5H, Cp2), 2.67 (m, 1H, H-6B), 2.49 (m, 1H, H-7A), 2.25 (m, 1H,
4.4.4. Preparation of (R,R,Sp,Sp)-5c
0
H-7B), 2.09 (m, 1H, H-8A), 2.05 (m, 2H, H-8B), 1.71 (m, 10H, H-7A ),
Trimethylaluminum (24.0 mg, 0.333 mmol, 1 eq) was dissolved
in dichloromethane (1 ml) and a solution of the diol (R,R,Sp,Sp)-3c
(179 mg, 0.333 mmol, 1 eq) in dichloromethane (4 ml) was added.
The mixture was stirred for 1 h, the solvent was removed and
pentane (4 ml) was added. Removal of the solvent in vacuo gave
complex (R,R,Sp,Sp)-5c as a pink solid (150 mg, 0.259 mmol, 77.9%).
X-ray quality crystals could be obtained by diffusion of pentane into
0
0
1.71 (m, 1H, H-7B ), 1.56 (m, 1H, H-8A ), 1.53 (m, 2H, H-8B ), 1.27 (d,
0
3J ¼ 6.1 Hz, 3H, CH13), 1.22 (d, 3J ¼ 6.1 Hz, 3H, CH13 ), 0.97 (d,
0
3J ¼ 6.1 Hz, 3H, CH32), 0.79 (d, 3J ¼ 6.1 Hz, 3H, CH23 ); 13C{1H} NMR
(126 MHz, CD2Cl2, 298 K, TMS):
d
¼ 165.1 (CHNB), 158.3 (CHNA),
134.2 (C-1A), 130.2 (C-1B), 77.4 (CH2), 76.9 (CH1), 71.7 (C-6B), 71.1 (C-
2A), 70.1 (Cp1), 69.6 (Cp2), 69.0 (C-6A), 66.3 (C-2B), 66.1 (C-4A), 64.9
(C-4B), 64.0 (C-5B), 62.6 (C-5A), 580.5 (C-3B), 57.2 (C-3A), 32.5 (C-7A),
a solution of (R,R,Sp,Sp)-5c in tetrahydrofurane at ꢁ30 ꢀC. M.p.:
0
28.8 (C-7B), 26.41, 26.38 (CH13, CH13 ), 25.9 (CH23 ), 25.61 (C-8B), 25.58
273 ꢀC (DSC); [
a
]
D
¼ ꢁ3100 (578 nm), þ596 (436 nm) (c ¼ 0.021,
20
(CH23), 25.1 (C-8A); IR (KBr):
n
bar ¼ 1610 cmꢁ1 (C]N); elemental
CH2Cl2); 1H NMR (600 MHz, CD2Cl2, 298 K, TMS):
d
¼ 8.63 (d,
analysis calcd (%) for C34H42Fe2N2O4Ti (702.27 g/mol): C, 58.15; H,
6.03; N, 3.99; found: C, 58.29; H, 6.08; N, 3.91.
4J ¼ 1.4 Hz,1H, CHNA), 8.22 (d, 4J ¼ 1.8 Hz,1H, CHNB), 4.46 (m, 2H, H-
3A, H-3B), 4.18 (t, 3J ¼ 2.8 Hz, 1H, H-4A), 4.14 (s, 5H, Cp1), 4.13 (dd,
3J ¼ 2.8 Hz, 4J ¼ 1.3 Hz, 1H, H-5A), 4.12 (dd, 3J ¼ 2.8 Hz, 4J ¼ 1.3 Hz,
1H, H-5B), 3.99 (t, 3J ¼ 2.8 Hz, 1H, H-4B), 3.96 (s, 5H, Cp2), 3.39 (m,
X-ray crystal structure analysis of (R,R,Sp,Sp)-4c: formula
C34H42Fe2N2O4Ti, M ¼ 702.30, red crystal 0.40 ꢃ 0.20 ꢃ 0.10 mm,
3
ꢀ
a ¼ 11.5364(1), b ¼ 11.9713(1), c ¼ 23.0457(3) A, V ¼ 3182.74(6) A ,
1H, H-6B), 2.70 (m, 1H, H-6A), 2.59 (m, 1H, H-7A), 2.29 (m, 1H, H-7B),
ꢀ
0
rcalc ¼ 1.466 g cmꢁ3
,
m
¼ 1.185 mmꢁ1, empirical absorption
2.12e2.03 (m, 2H, H-8A, H-8B), 1.52 (m, 1H, H-7A ), 1.49 (m, 4H, H-
0
0
0
correction (0.649 ꢄ T ꢄ 0.891), Z ¼ 4, orthorhombic, space group
7B ), 1.53, 1.50 (m, 2H, H-8A , H-8B ), ꢁ1.01 (s, 3H, AlCH3); 13C{1H}
P212121 (No. 19),
l
¼ 0.71073 A, T ¼ 223(2) K,
)/
u
and
4
scans, 21 508
ꢀꢁ1
NMR (151 MHz, CD2Cl2, 298 K, TMS): d
¼ 174.7 (CHNA), 162.6
ꢀ
reflections collected (ꢂh, ꢂk, ꢂl), [(sin
q
l
] ¼ 0.66 A , 7345
(CHNB), 133.3 (C-1A), 131.9 (C-1B), 69.99, 69.95 (Cp1, Cp2), 67.4 (C-
6A), 66.8 (C-4A), 64.9 (C-4B), 62.7 (C-2B), 62.4 (C-5B), 61.90, 61.88 (C-
5A, C-6B), 60.9 (C-3B), 60.4 (C-2A), 60.0 (C-3A), 30.6 (C-7A), 27.6 (C-
independent (Rint ¼ 0.040) and 6307 observed reflections [I ꢅ 2
s
(I)], 392 refined parameters, R ¼ 0.033, wR2 ¼ 0.079, Flack
parameter ꢁ0.018(13), max. (min.) residual electron density 0.58
7B), 24.8 (C-8B), 24.3 (C-8A), ꢁ6.1 (br, AlCH3); IR (KBr):
n
ꢀꢁ3
(ꢁ0.32) e A , hydrogen atoms calculated and refined as riding
bar
¼
1630 cmꢁ1 (C]N); elemental analysis calcd (%) for
atoms. CCDC 762152.
C29H31AlFe2N2O2 (578.24 g/mol): C, 60.24; H, 5.40; N, 4.84; found:
C, 59.47; H, 5.26; N, 4.94.
4.4.3. Preparation of (S,S,Sp,Sp)-5b
X-ray crystal structure analysis of (R,R,Sp,Sp)-5c: formula
Trimethylaluminium (12.9 mg, 0.179 mmol, 1 eq) was dissolved
in dichloromethane (1 ml) and a solution of the diol (S,S,Sp,Sp)-3b
(96.3 mg, 0.179 mmol, 1 eq) in dichloromethane (4 ml) was added.
The mixture was stirred for 1 h, the solvent was removed and
pentane (2 ml) was added. Removal of the solvent in vacuo gave
complex (S,S,Sp,Sp)-5b as a pink solid (75.1 mg, 0.130 mmol, 72.6%).
X-ray quality crystals could be obtained by diffusion of pentane into
C29H31AlFe2O2N2$2C4H8O,
M
¼
722.45,
red
crystal
ꢀ
0.45 ꢃ 0.10 ꢃ 0.10 mm, a ¼ 13.063(2), c ¼ 20.881(2) A, V ¼ 3563.2
3
(8) A , rcalc ¼ 1.347 g cmꢁ3
,
m
¼ 7.088 mmꢁ1, empirical absorption
ꢀ
correction (0.143 ꢄ T ꢄ 0.538), Z ¼ 4, tetragonal, space group P43
ꢀ
(No. 78),
l
¼ 1.54178 A, T ¼ 223(2) K,
u
and
4 scans, 11 731 reflec-
ꢀꢁ1
tions collected (ꢂh, ꢂk, ꢂl), [(sin
q)/
l] ¼ 0.60 A , 4043 independent
(Rint ¼ 0.096) and 2493 observed reflections [I ꢅ 2
s(I)], 358 refined
a solution of (S,S,Sp,Sp)-5b in tetrahydrofurane at ꢁ30 ꢀC. M.p.:
parameters, R ¼ 0.087, wR2 ¼ 0.244, Flack parameter 0.055(16),
20
ꢀꢁ3
277 ꢀC (DSC); [
a]
D
¼ ꢁ3410 (578 nm), þ1450 (436 nm) (c ¼ 0.021,
max. (min.) residual electron density 0.40 (ꢁ0.39) e A , hydrogen
CH2Cl2); 1H NMR (600 MHz, CD2Cl2, 298 K, TMS):
d
¼ 8.55 (d,
atoms calculated and refined as riding atoms, due to crystal shape
and disordered solvent molecules the quality of the analysis is poor.
CCDC 762155.
4J ¼ 1.9 Hz,1H, CHNA), 8.36 (d, 4J ¼ 1.9 Hz,1H, CHNB), 4.63 (m, 1H, H-
3A), 4.59 (m, 1H, H-3B), 4.28 (s, 5H, Cp1), 4.21 (m, 1H, H-5B), 4.21 (m,
2H, H-5B), 4.21 (s, 5H, Cp2), 4.20 (t, 3J ¼ 2.7 Hz, 1H, H-4A), 4.17 (t,
3J ¼ 2.7 Hz, 1H, H-4B), 3.38 (m, 1H, H-6B), 2.79 (m, 1H, H-6A), 2.49
(m, 1H, H-7B), 2.35 (m, 1H, H-7A), 2.09 (m, 1H, H-8B), 2.07 (m, 1H, H-
4.4.5. Preparation of (S,S,Sp,Sp)-6b
The diol (S,S,Sp,Sp)-3b (102 mg, 0.190 mmol, 1 eq) was dissolved
in dichloromethane (5 ml) and diethylaluminumchloride was
0
0
0
8A), 1.52 (m,01H, H-8B ), 1.45 (m, 1H, H-8A ), 1.41 (m, 1H, H-7B ), 1.39
(m, 1H, H-7A ), ꢁ0.92 (s, 3H, AlCH3); 13C{1H} NMR (151 MHz, CD2Cl2,
added (199 ml of a 1 M solution in hexanes, 0.199 mmol, 1.05 eq).
298 K, TMS):
d
¼ 170.4 (CHNA), 166.6 (CHNB), 133.8 (C-1A), 131.5 (C-
The mixture was stirred overnight and filtered. Removal of the
solvent gave complex (S,S,Sp,Sp)-6b as a pink solid (90.7 mg,
0.152 mmol, 80.2%). X-ray quality crystals could be obtained by
1B), 69.84, 69.81 (Cp1, Cp2), 66.5 (C-4A), 66.1 (C-6A), 65.2 (C-4B), 62.8
(C-6B), 62.5 (C-5A), 62.4 (C-2A), 61.8 (C-2B), 61.7 (C-5B), 60.6 (C-3B),
60.3 (C-3A), 29.9 (C-7B), 27.8 (C-7A), 24.7 (C-8A), 24.3 (C-8B), ꢁ6.8
diffusion of pentane into a solution of (S,S,Sp,Sp)-6b in tetrahy-
20
(br, AlCH3); IR (KBr):
n
bar ¼ 1631 cmꢁ1 (C]N); elemental analysis
drofurane at ꢁ30 ꢀC. M.p.: 262 ꢀC (DSC); [
a]
¼ þ1780 (436 nm,
D
calcd (%) for C29H31AlFe2N2O2 (578.24 g/mol): C, 60.24; H, 5.40; N,
4.84; found: C, 59.63; H, 5.33; N, 4.73.
c ¼ 0.020, CH2Cl2); 1H NMR (600 MHz, CD2Cl2, 188 K, TMS):
¼ 8.53
d
(bs, 1H, CHNA), 8.40 (bs, 1H, CHNB), 4.55 (bs, 1H, H-3A), 4.47 (bs, 1H,
H-3B), 4.19 (bs, 5H, Cp1), 4.17 (bs, 1H, H-5A), 4.15 (bs, 1H, H-5B), 4.11
(bs,1H, H-4A), 4.07 (bs, 1H, H-4B),1 4.06 (bs, 5H, Cp2), 3.42 (m,1H, H-
6B), 2.84 (m, 1H, H-6A), 2.44 (m, 1H, H-7A), 2.32 (m, 1H, H-7B),
X-ray crystal structure analysis of (S,S,Sp,Sp)-5b: formula
C29H31AlFe2O2N2$2C4H8O,
M
¼
722.45,
red
crystal
ꢀ
0.30 ꢃ 0.04 ꢃ 0.03 mm, a ¼ 12.6911(6), c ¼ 21.7816(9) A, V ¼ 3508.2
0
0
0
3
(3) A , rcalc ¼ 1.368 g cmꢁ3
,
m
¼ 7.199 mmꢁ1, empirical absorption
2.00e1.90 (m, 2H, H-8A, H-8B), 1.43e1.26 (m, 4H, H-7A , H-7B , H-8A ,
ꢀ
0
correction (0.221 ꢄ T ꢄ 0.813), Z ¼ 4, tetragonal, space group P43 (No.
H-8B ), [all resonances were broad]; 13C{1H} NMR (151 MHz, CD2Cl2,
ꢀ
78),
collected (ꢂh, ꢂk, ꢂl), [(sin
(Rint ¼ 0.093) and 2882 observed reflections [I ꢅ 2
l
¼ 1.54178 A, T ¼ 223(2) K,
u
and
] ¼ 0.60 A , 4347 independent
(I)], 358 refined
4
scans, 14 408 reflections
ꢀꢁ1
q)/
l
1
s
The signal of H-4B appears as a shoulder within the signal of Cp2.