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J. Claffey et al. / Journal of Organometallic Chemistry 695 (2010) 2105e2117
a brown solution, which was refluxed for 16 h, then cooled and the
solvent was removed under reduced pressure. The remaining
brown residue was extracted with trichloromethane (120 mL) and
filtered through celite to remove the remaining LiCl. The brown
filtrate was filtered twice more by gravity filtration. The solvent was
removed under reduced pressure to yield 0.95 g of a brown/black
solid (1.7 mmol, 56.7% yield).
of the lithium cyclopentadienide intermediate and the solution had
changed colour from orange/red to colourless. The solvent was
decanted off, the precipitate dried under reduced pressure and
transferred into a Schlenk flask under nitrogen. 1.15 g (5.24 mmol,
73.2% yield) of 7c was obtained, dissolved in 60 mL of THF and
2.6 mL (2.6 mmol) of titanium tetrachloride was added to give
a brown solution, which was refluxed for 16 h. The solution was
then cooled and the solvent was removed under reduced pressure.
The remaining brown residue was extracted with trichloromethane
(90 mL) and filtered through celite to remove the remaining LiCl.
The orange filtrate was filtered twice more by gravity filtration. The
solvent was removed under reduced pressure to yield 0.85 g of an
orange solid (1.6 mmol, 61.5% yield).
1H NMR
(d ppm CDCl3, 400 MHz): 7.27 [4H, d, J 8.2,
C6H4eCH2eOCH2CH3], 7.19 [4H, d, J 7.6, C6H4eCH2eOCH2CH3], 6.31
[8H, s, C5H4], 4.47 [4H, s, C6H4eCH2eOCH2CH3], 4.08 [4H, s,
C5H4eCH2], 3.53 [4H, q, J 8.0, 6.8, C6H4eCH2eOCH2CH3],1.23 [6H, m,
C6H4eCH2eOCH2CH3]. 13C NMR (
d
ppm CDCl3, 100 MHz, proton
decoupled): 137.8, 136.1, 135.8, 128.0, 127.0, 121.5, 114.8, 71.4
[C6H4eCH2eOCH2CH3], 64.7 [C6H4eCH2eOCH2CH3], 35.7
1H NMR (
d, J 8.0, C6H4], 6.22 [8H, m, C5H4eCH2], 4.16 [4H, s, C5H4eCH2], 3.42
[4H, s, CH2N(CH3)2], 2.71 [12H, s, CH2N(CH3)2]. 13C NMR (
ppm D2O,
d ppm D2O, 400 MHz): 7.46 [4H, d, J 8.0, C6H4], 7.28 [4H,
[C5H4eCH2], 14.2 [C6H4eCH2eOCH2CH3]. IR absorptions (KBr,
cmꢂ1): 2967, 2917, 2854, 2306, 1701, 1607, 1262, 1099, 1021, 805.
d
UVeVis (CH2Cl2, nm): 215 (
3
3500), 230 (
3
3700), 255 (
3
3500), 313 (
3
100 MHz, proton decoupled): 140.9, 138.5, 131.2, 130.1, 127.3, 121.5,
117.5, 55.0, 45.8, 41.8. IR absorptions (KBr, cmꢂ1): 2963, 2925, 2700,
2362, 2114, 1615, 1516, 1262, 1095, 1020, 943, 863, 804. UVeVis
1600), lmax 372 (
3
680). ES-MS (pos) in CH2Cl2: 509.1 ([M ꢂ Clꢂ]þ).
Analysis Calculated for TiC30O2H34Cl2: C, 66.07%; H, 6.28%; Cl,
13.00%; Found C, 64.98%; H, 6.03%; Cl, 12.74%.
(H2O, nm): 215 (3 1100), 230 (3 1400), 255 (3 1300), lmax 320 (3 730)
ES-MS (pos) in H2O: 507.9 ([M ꢂ Clꢂ]þ). Analysis Calculated for
TiC30N2H36Cl2: C, 66.31%; H, 6.68%; N, 5.16%; Cl, 13.05%; Found C,
66.45%; H, 6.26%; N, 4.78%, Cl, 13.37%.
2.2.10. 6(4-Dimethylaminomethyl-phenyl) fulvene,
C5H4eCHeC6H4eCH2N(CH3)2 (6c)
4.02 g (24.6 mmol) of 5c was dissolved in 150 mL of methanol
to give a colourless solution. 4.0 mL (49 mmol) of freshly cracked
cyclopentadiene was added to the reaction solution, which
remained colourless. 3.1 mL (37 mmol) pyrrolidine was added to
the solution. The solution immediately changed colour from col-
ourless to yellow and finally reached a red colour. The reaction was
left to stir whilst being monitored by thin layer chromatography
(alumina/dichloromethane), which showed only one product spot
after 6 h. 3.5 mL of acetic acid was added to quench the reaction.
100 mL of water was added to the reaction mixture and the
solution was brought to a basic pH through the addition of solid
NaOH. The organic product was extracted by 3 ꢁ 50 mL diethyl
ether fractions. The ether fractions were combined and the solu-
tion was dried over magnesium sulphate and had its solvent
removed at reduced pressure to yield a red oil. The red oil was
purified by alumina column chromatography with 10:1 pentane/
dichloromethane used as the eluent. The solvent was removed at
reduced pressure to yield 1.83 g (35.4% yield, 8.66 mmol) of a red
solid.
2.2.12. 6(4-Diethylaminomethyl-phenyl) fulvene,
C5H4eCHeC6H4eCH2N(CH2CH3)2 (6d)
3.00 g (15.6 mmol) of 5d was dissolved in 100 mL of methanol to
give a colourless solution. 4.0 mL (49 mmol) of freshly cracked
cyclopentadiene was added to the reaction solution, which
remained colourless. 3.1 mL (37 mmol) pyrrolidine was added to
the solution. The solution immediately changed colour from col-
ourless to yellow and finally reached a red colour. The reaction was
left to stir whilst being monitored by thin layer chromatography
(alumina/dichloromethane), which showed only one product spot
after 8 h. 2.5 mL of acetic acid was added to quench the reaction.
150 mL of water was added to the reaction mixture and the solution
was made basic through the addition of 5 M NaOH. The organic
product was extracted by 3 ꢁ 50 mL ethyl acetate. The ethyl acetate
fractions were combined and the solution was dried over magne-
sium sulphate and had its solvent removed at reduced pressure to
yield a red oil. The red oil was purified by alumina column chro-
matography with 5:1 pentane/dichloromethane used as the eluent.
The solvent was removed at reduced pressure to yield 3.34 g (89.7%
yield, 14.0 mmol) of a red oil.
1H NMR (
d ppm CDCl3, 400 MHz): 7.54 [C6H4, 2H, d, J 8.1], 7.34
[C6H4, 2H, d, J 8.1], 7.19 [C5H4eCH2, 1H, s], 6.66 [C5H4, 2H, m], 6.39
[C5H4, 2H, m], 3.43 [CH2eN(CH3)2, 2H, s], 2.24 [CH2eN(CH3)2, 6H, s].
1H NMR (
d ppm CDCl3, 400 MHz): 7.54 [2H, d, J 8.1, C6H4eCH2N
13C NMR (
d
ppm CDCl3, 100 MHz, proton decoupled): 144.9, 140.3,
(CH2CH3)2], 7.38 [2H, d, J 8.1, C6H4eCH2N(CH2CH3)2], 7.20 [1H, s,
C5H4eCH], 6.67 [2H, m, C5H4eCH], 6.50 [1H, d, J 5.1, C5H4eCH], 6.32
[1H, dt, J 5.1, 1.7, C5H4eCH], 3.59 [2H, s, C6H4eCH2N(CH2CH3)2], 2.53
[4H, q, J 7.2, 7.2, C6H4eCH2N(CH2CH3)2],1.04 [6H, t, J 7.2, C6H4eCH2N
138.1, 135.6, 135.3, 130.7, 130.6, 129.4, 127.3, 120.3, 64.1 [CH2eN
(CH3)2], 45.5 [CH2eN(CH3)2],. IR absorptions (CH2Cl2, cmꢂ1): 3012,
2957, 1866, 1841, 1769, 1740, 1648, 1558, 1537, 1497, 1454, 1079, 860,
757, 660. UVeVis (CH2Cl2, nm): 235 (
330 ( 11 000). Analysis Calculated for C15NH17: C, 85.26%; H, 8.11%;
N, 6.63%; Found C, 85.29%; H, 8.08%; N, 6.89%.
3
4300), 315 (
3
10 000), lmax
(CH2CH3)2]. 13C NMR (
d
ppm CDCl3, 100 MHz, proton decoupled):
3
144.7, 141.6, 138.3, 135.3, 135.2, 130.6, 130.5, 129.1, 127.3, 120.3, 57.3
[C6H4eCH2N(CH2CH3)2],
46.9
[C6H4eCH2N(CH2CH3)2],
11.8
[C6H4eCH2N(CH2CH3)2]. IR absorptions (CH2Cl2, cmꢂ1): 2964, 1786,
2.2.11. Bis-[(4-dimethylaminomethyl-benzyl)cyclopentadienyl]
1734, 1679, 1651, 1554, 1540, 1502, 1306, 1243, 1001, 831, 644.
UVeVis (CH2Cl2, nm): 234 (3 4400), lmax 320 (3 10 000). Analysis
titanium(IV) dichloride, [(
h
5-C5H4eCH2eC6H4eCH2N(CH3)2)2]2TiCl2
(8c)
Calculated for C17NH21: C, 85.31%; H, 8.84%; N, 5.85%; Found C,
85.46%; H, 8.59%; N, 5.59%.
9.0 mL (9.0 mmol) of 1 M solution of Super Hydride (LiBEt3H) in
THF was concentrated by removal of the solvent by heating it to
60 ꢃC under reduced pressure of 10ꢂ2 mbar for 20 min and then to
90 ꢃC for 10 min in a Schlenk flask. The concentrated Super Hydride
was dissolved in 30 mL of pentane to give a cloudy white suspen-
sion. 1.50 g (7.10 mmol) of 6c was added to a Schlenk flask and was
dissolved in 60 mL pentane to give a red solution. The red fulvene
solution was transferred to the Super Hydride solution via cannula.
The solution was left to stir for 6 h to give a pale yellow precipitate
2.2.13. Bis-[(4-diethylaminomethyl-benzyl)cyclopentadienyl]
titanium(IV) dichloride, [(h
5-C5H4eCH2eC6H4eCH2N
(CH2CH3)2)2]2TiCl2 (8d)
14.0 mL (14.0 mmol) of 1 M solution of Super Hydride (LiBEt3H)
in THF was concentrated by removal of the solvent by heating it to
60 ꢃC under reduced pressure of 10ꢂ2 mbar for 20 min and then to
90 ꢃC for 10 min in a Schlenk flask. The concentrated Super Hydride