J.A. Mata et al. / Journal of Organometallic Chemistry 616 (2000) 80–88
87
(cm−1): 2218 (s), 1248 (w). Anal. Calc. for compound
6-(E,E,Z), C35H27F6FeN (Mw=517.45): C, 81.20; H,
5.26; N, 2.71. Found: C, 81.84; H, 5.63; N, 2.73%.
Electrospray MS. Cone 77 V. m/z (fragment): 517, M+.
219.1 (1C, CO). IR (cm−1): 2209 (s), 2074 (s), 1934
(vs). Anal. Calc. for compound 9-(E,Z),
C32H21FeNO5Cr (Mw=607.37): C, 63.30; H, 3.45; N,
2.31. Found: C, 61.7; H, 3.83; N, 2.29%.
1H-NMR for compound 9-(E,E) (500 MHz, CDCl3):
l 7.64 (d, 2H, 3JH–H=8.0 Hz, C6H4); 7.57 (d, 2H,
3JH–H=8.0 Hz, C6H4); 7.51 (d, 2H, 3JH–H=7.5 Hz,
4.7. Syntheses of the compound 6-(E,E,E)
3
This compound was obtained following the general
procedure described for compound 5-(E,E) and using
the aldehyde 2-(E) (1.6 g, 5.0 mmol) instead of 1.
Purification was made by column chromatography on
silica gel using hexane–CH2Cl2 (1:4) as eluent. 1H-
C6H4); 7.46 (d, 2H, JH–H=7.5 Hz, C6H4); 7.24 (d, 1H,
3
3JH–H=16.0 Hz, CHꢀCH); 7.09 (d, 1H, JH–H=16.5
3
Hz, CHꢀCH); 6.95 (d, 1H, JH–H=16.0 Hz, CHꢀCH);
3
6.71 (d, 1H, JH–H=15.5 Hz, CHꢀCH); 4.49 (s, 2H,
C5H4); 4.33 (s, 2H, C5H4); 4.16 (s, 5H, C5H5). 13C-
NMR (300 MHz, CDCl3): l 67.7, 69.9 (4C, C5H4); 69.9
(5C, C5H5); 83.7 (1Cq, C5H4); 108.7 (1C, CN); 125.8,
126.1, 126.8, 127.3, 127.9, 132.7, 133.0, 133.3 (12C,
CHꢀCH and C6H4); 128.8, 135.2, 139.1, 143.4 (4Cq,
C6H4); 214.4 (4C, CO); 219.7 (1C, CO). IR (cm−1):
2213 (s), 2074 (s), 1942 (vs). Anal. Calc. for compound
9-(E,E), C32H21FeNO5Cr (Mw=607.37): C, 63.30; H,
3.45; N, 2.31. Found: C, 62.6; H, 3.50; N, 2.32%.
Electrospray MS. Cone 27 V. m/z (fragment): 607, M+.
3
NMR (500 MHz, CDCl3): l 7.64 (d, 2H, JH–H=8.0
3
Hz, C6H4); 7.58 (d, 2H, JH–H=8.0 Hz, C6H4); 7.43 (d,
3
3
2H, JH–H=8.0 Hz, C6H4); 7.34 (d, 2H, JH–H=8.0
3
Hz, C6H4); 7.32 (d, 2H, JH–H=8.5 Hz, C6H4); 7.26 (d,
3
3
2H, JH–H=8.0 Hz, C6H4); 7.19 (d, 1H, JH–H=16.0,
3
CHꢀCH); 7.08 (d, 1H, JH–H=17.0, CHꢀCH); 6.88 (d,
3
3
1H, JH–H=16.0, CHꢀCH); 6.68 (d, 1H, JH–H=16.0,
3
CHꢀCH); 6.62 (d, 1H, JH–H=17.0, CHꢀCH); 6.59 (d,
3
1H, JH–H=17.0, CHꢀCH); 4.47 (s, 2H, C5H4); 4.30 (s,
2H, C5H4); 4.15 (s, 5H, C5H5).13C-NMR (500 MHz,
CDCl3): l 67.6, 70.0 (4C, C5H4); 69.9 (5C, C5H5); 83.7
(1Cq, C5H4); 111.2 (1C, CN); 126.3, 127.2, 127.4, 127.6,
127.9, 130.0, 130.2, 131.4, 132.8, 133.0, 133.8 (18C,
CHꢀCH and C6H4); 119.5, 135.8, 136.3, 137.7, 138.7,
142.6 (6Cq, C6H4). IR (cm−1): 2211 (s), 1308 (w).
Electrospray MS. Cone 76 V. m/z (fragment): 517, M+.
4.9. Syntheses of 10-(E,E) and 10-(E,Z)
These compounds were obtained using the general
procedure described for 9 but using tungsten hexacar-
bonyl (281.5 mg, 0.8 mmol) instead of chromium hex-
acarbonyl. Yield for compound 10-(E,Z) 40% and for
compound 10-(E,E) 70%.
4.8. Syntheses of the compounds 9-(E,E) and 9-(E,Z)
1H-NMR for compound 10-(E,Z) (300 MHz,
3
CDCl3): l 7.57 (d, 2H, JH–H=8.7 Hz, C6H4); 7.45 (d,
3
3
Chromium hexacarbonyl (176 mg, 0.8 mmol) was
dissolved in THF (30 ml) and the resulting solution was
irradiated using a Hg lamp for 1 h. Compound 5-(E,Z)
(150 mg, 0.4 mmol) or compound 5-(E,E) (150 mg, 0.4
mmol) were added to the yellow solution formed upon
irradiation in order to obtain compounds 9-(E,Z) or
9-(E,E), respectively. The reaction mixture was stirred
for another 30 min, filtered to remove the solid, and the
solvent was removed under reduced pressure. Purifica-
tion by column chromatography on neutral alumina
with CH2Cl2–hexane (1:1) afforded pure compounds
9-(E,Z) yield 40% or 9-(E,E) yield 60%.
2H, JH–H=8.1 Hz, C6H4); 7.32 (d, 2H, JH–H=8.1
3
Hz, C6H4); 7.16 (d, 2H, JH–H=8.1 Hz, C6H4); 6.90 (d,
3
3
1H, JH–H=16.2 Hz, CHꢀCH); 6.66 (d, 1H, JH–H
=
16.2 Hz, CHꢀCH); 6.78 (d, 1H, 3JH–H=12.0 Hz,
3
CHꢀCH); 6.58 (d, 1H, JH–H=12.0 Hz, CHꢀCH); 4.47
3
3
(t, 2H, JH–H=1.8 Hz, C5H4); 4.32 (t, 2H, JH–H=1.8
Hz, C5H4); 4.15 (s, 5H, C5H5). 13C-NMR (500 MHz,
CDCl3): l 67.7, 69.9 (4C, C5H4); 69.9 (5C, C5H5); 83.7
(1Cq, C5H4); 108.7 (1C, CN); 125.9, 126.5, 128.2, 128.7,
129.9, 130.6, 133.3, 134.7 (12C, CHꢀCH and C6H4);
125.4, 134.9, 138.5, 144.6 (4Cq, C6H4); 197.0 (4C, CO);
200.7 (1C, CO). IR (cm−1): 2073 (s), 1928 (vs). Anal.
Calc. for compound 10-(E,Z), C32H21FeNO5W (Mw=
739.23): C, 52.00; H, 2.86; N, 1.89. Found: C, 52.03; H,
2.99; N, 1.91%.
1H-NMR for compound 9-(E,Z) (300 MHz, CDCl3):
l 7.54 (d, 2H, 3JH–H=8.4 Hz, C6H4); 7.39 (d, 2H,
3JH–H=8.4 Hz, C6H4); 7.32 (d, 2H, 3JH–H=8.4 Hz,
3
C6H4); 7.17 (d, 2H, JH–H=8.1 Hz, C6H4); 6.72 (d, 1H,
1H-NMR for compound 10-(E,E) (500 MHz,
3
3
3JH–H=16.2 Hz, CHꢀCH); 6.49 (d, 1H, JH–H=16.2
CDCl3): l 7.68 (d, 2H, JH–H=8.5 Hz, C6H4); 7.65 (d,
3
3
3
Hz, CHꢀCH); 6.55 (d, 1H, JH–H=12.0 Hz, CHꢀCH);
2H, JH–H=8.0 Hz, C6H4); 7.52 (d, 2H, JH–H=8.0
3
3
6.38 (d, 1H, JH–H=12.0 Hz, CHꢀCH); 4.47 (t, 2H,
Hz, C6H4); 7.47 (d, 2H, JH–H=8.0 Hz, C6H4); 7.27 (d,
3JH–H=1.8 Hz, C5H4); 4.31 (t, 2H, 3JH–H=1.8 Hz,
C5H4); 4.15 (s, 5H, C5H5). 13C-NMR (300 MHz,
CDCl3): l 67.9, 69.9 (4C, C5H4); 69.9 (5C, C5H5); 83.7
(1Cq, C5H4); 109.5 (1C, CN); 125.8, 126.4, 128.5, 129.8,
130.1, 130.4, 132.7, 132.9 (12C, CHꢀCH and C6H4);
129.1, 134.3, 138.3, 143.9 (4Cq, C6H4); 214.3 (4C, CO);
1H, JH–H=16.5 Hz, CHꢀCH); 7.11 (d, 1H, JH–H=
3
3
16.5 Hz, CHꢀCH); 6.95 (d, 1H, 3JH–H=16.5 Hz,
3
CHꢀCH); 6.72 (d, 1H, JH–H=16.0 Hz, CHꢀCH); 4.49
(s, 2H, C5H4); 4.33 (s, 2H, C5H4); 4.16 (s, 5H, C5H5).
13C-NMR (300 MHz, CDCl3): l 67.7, 70.1 (4C, C5H4);
69.9 (5C, C5H5); 83.7 (1Cq, C5H4); 108.5 (1C, CN);