J.-Y. The´pot, C. Lapinte / Journal of Organometallic Chemistry 656 (2002) 146ꢁ
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153
1
3.3.1. 3a3 (1.065 g, 1.6 mmol, 80%)
IR (cmꢂ1, CH2Cl2) 1610 (Ph), 1995 (CO), 2037 (CO).
C5(C6H3Me2)5), 129.7 (dm, JCÃH
ꢀ
/
155 Hz, p-
C6H3Me2), 129.9 (s, ipso-C6H3Me2), 130.4 (dq,
3
1H-NMR (300 MHz, CDCl3) 2.06 (s, 6H, Me), 6.67ꢁ
/
1JCÃH
2JCÃH
ꢀ
/
159 Hz, JCÃH
6 Hz, m-C6H3Me2), 214.4 (s, CO). FABHRMS
ꢀ
/
5 Hz, o-C6H3Me2), 136.6 (q,
7.23 (m, 23H, Ph). 13C-NMR (75 MHz, CDCl3) 21.3 (q,
1JCÃH
126 Hz, Me), 100.3 (s, C ÃPh), 101.7 (s, C Ã
C6H3Me2), 101.9 (s, CÃ Ph), 127.81 (d, JCÃH
ꢀ
/
79 56
ꢀ
/
/
/
Calc. for [C45H45 Br Fe+ꢃ] ([MÃ
/
2CO+ꢃ]): 720.2054.
1
/
ꢀ
/
161
161 Hz, o-Ph), 128.48
162 Hz, p-Ph), 128.52 (d, 1JCÃH
162 Hz, p-
Found: 720.2061.
1
Hz, o-Ph), 127.83 (d, JCÃH
(d, 1JCÃH
ꢀ
/
ꢀ
/
ꢀ
/
3.3.5. 3b4 (1.20 g, 1.5 mmol, 75%)
Ph), 129.3, 130.0, 130.1 (3 s, ipso-Ph, C6H3Me2), 130.2
(m, o-C6H3Me2, p-C6H3Me2), 130.3 (m, o-C6H3Me2, p-
IR (cmꢂ1, CH2Cl2) 1601 (Ph), 1992 (CO), 2034 (CO).
1H-NMR (300 MHz, CDCl3) 1.53 (s, 3H, Me), 1.95 (s,
12H, Me), 2.10 (s, 12H, Me), 2.31 (s, 3H, Me), 6.49 (m,
4H, o-3,5-C6H3Me2); 6.72 (m, 2H, p-3,5-C6H3Me2),
6.78 (m, 4H, o-3,5-C6H3Me2), 6.85 (m, 2H, p-3,5-
C6H3Me2), 6.93, 7.01, 7.76 (3 m, 3x1H, o,m,p-2,5-
1
C6H3Me2), 132.4 (d, JCÃH
ꢀ161 Hz, m-Ph), 132.5 (d,
/
2
1JCÃH
ꢀ
/
161 Hz, m-Ph), 137.1 (q, JCÃH
ꢀ5 Hz, m-
/
C6H3Me2), 213.8 (s, CO). Anal. Calc. for
C39H29BrFeO2: C, 70.40; H, 4.39. Found: C, 70.44; H
4.49%.
C6H3Me2). 13C-NMR (75 MHz, CDCl3) 19.9 (q,
1JCÃH
ꢀ
/
125 Hz, o-2,5-C6H3Me2), 21.2 (q, JCÃH
ꢀ125
/
1
3.3.2. 3a7 (0.810 g, 1.2 mmol, 60%)
IR (cmꢂ1, CH2Cl2) 2001 (CO), 2041 (CO). 19F-NMR
Hz, other Me), 97.5 (s, C Ã
3,5-C6H3Me2), 107.0 (s, C Ã
dm, ipso,p-3,5-C6H3Me2), 129.8 (dm, JCÃH
/
2,5-C6H3Me2), 97.9 (s, C Ã
/
/
3,5-C6H3Me2), 129.4 (sꢃ
/
3
1
(282 MHz, CDCl3) 109.70 (t, JFÃH
ꢀ
/
8 Hz). 13C-NMR
ꢀ
/
160 Hz,
160 Hz, o-3,5-
160 Hz, o-3,5-
C6H3Me2), 130.4 (s, ipso-3,5-C6H3Me2), 130.9 (s, ipso-
1
(75 MHz, CDCl3) 99.6 (s, C Ã
/
C6H3F2), 100.2 (s, C Ã
/
p-3,5-C6H3Me2), 129.9 (dm, JCÃH
C6H3Me2), 130.2 (dm, 1JCÃH
ꢀ
/
1
C6H5), 102.0 (s, C ÃC6H5), 104.2 (dt, JCÃH
/
ꢀ
/
160 Hz,
160 Hz,
160 Hz, o-
ꢀ
/
2JCÃF
2JCÃF
ꢀ
/
23 Hz, p-C6H3F2), 115.6 (dd, JCÃH
ꢀ
/
1
1
ꢀ
/
26 Hz, o-C6H3F2), 127.9 (d, 1JCÃH
ꢀ
/
2,5-C6H3Me2), 134.5 (dm, JCÃH
C6H3Me2), 134.8 (m, 2,5-C6H3Me2), 135.8 (m, 2,5-
ꢀ160 Hz, 2,5-
/
1
C6H5), 128.7 (d, JCÃH
ꢀ160 Hz, p-C6H5), 132.2 (d,
/
1JCÃH
162.1 (dm, JCÃF
ꢀ
/
160 Hz, m-C6H5), 133.9 (m, ipso-C6H3F2),
1
C6H3Me2), 136.2 (q, JCÃH
ꢀ6 Hz, m-3,5-C6H3Me2),
/
2
1
2
ꢀ/248 Hz, m-C6H3F2), 213.2 (s, CO);
136.9 (q, JCÃH
ꢀ
/
160 Hz, JCÃH
ꢀ
/
6 Hz, m-3,5-
C6H3Me2), 214.4 (s, CO). FABHRMS Calc. for
FABHRMS Calc. for [C35H2379BrF256Fe]ꢃ ([MÃ
/
2CO]+ꢃ): 616.0303. Found: 616.0300.
[C45H45 Br Fe+ꢃ] ([MÃ
720.2055.
/
2CO+ꢃ]): 720.2054. Found:
79 56
3.3.3. 3b2 (1.260 g, 1.6 mmol, 80%)
IR (cmꢂ1, CH2Cl2) 1601 (Ph), 1994 (CO), 2036 (CO).
1H-NMR (300 MHz, CDCl3) 2.05 (s, 12H, CH3), 2.06 (s,
12H, CH3), 2.11 (s, 3H, CH3), 6.68 (s, 8H, o-C6H3Me2),
3.3.6. 3b6 (1.105 g, 1.45 mmol, 72%)
IR (cmꢂ1, CH2Cl2) 1603 (Ph), 1994 (CO), 2036 (CO).
1H-NMR (300 MHz, CDCl3) 2.05 (s, 12H, Me), 6.66 (s,
6.81 (s, 4H, p-C6H3Me2), 6.93, 7.00 (2 d, 2H, C6H4Me).
8H, o-C6H3Me2), 6.81 (s, 4H, p-C6H3Me2), 6.9ꢁ7.0 (m,
/
1
13C-NMR (75 MHz, CDCl3) 21.1 (q, JCÃH
ꢀ
/
126 Hz,
C6H4F). 19F-NMR (282 MHz, CDCl3) 113.9 (m,
C6H4F). 13C-NMR , 75 MHz, CDCl3) 21.1 (q,
C6H3Me2), 21.3 (q, 1JCÃH
C ÃC6H3Me2), 101.0 (s, C Ã
C6H4Me), 127.3 (d, JCÃH
ꢀ
/
126 Hz, C6H4Me), 100.7 (s,
C6H3Me2), 101.5 (s, C Ã
160 Hz, m-C6H4Me),
154 Hz, p-C6H4Me), 129.5 (dm, o-
/
/
/
1JCÃH
C6H3Me2), 102.3 (s, C Ã
ꢀ
/
127 Hz, Me), 99.7 (s, C Ã
/
C6H4F), 100.0 (s, C Ã
/
1
ꢀ
/
/
C6H3Me2), 115.07 (ddm,
1
2
128.8 (dm, JCÃH
ꢀ
/
1JCÃH
ꢀ
/
160 Hz, JCÃF
ꢀ/21,3 Hz, p-C6H4F), 119.3
1
1
2
C6H4Me), 129.7 (dm, JCÃH
ꢀ
/
150 Hz, p-C6H3Me2),
150 Hz, p-C6H3Me2), 129.8 (s,
ipso-C6H3Me2), 129.9 (s, ipso-C6H3Me2), 130.3 (d,
(ddm, JCÃH
ꢀ
/
161 Hz, JCÃF
ꢀ22.9 Hz, o-C6H4F),
/
1
1
4
129.8 (dm, JCÃH
ꢀ
/
128.5 (ddm, JCÃH
ꢀ
/
160 Hz, JCÃF
ꢀ
/
2.44 Hz, o-
160Hz, JCÃF 8.55 Hz,
m-C6H4F), 129.36 (s, ipso-C6H3Me2), 129.56 (s, ipso-
1
4
C6H4F), 129.0 (ddm, JCÃH
ꢀ
/
ꢀ
/
3JCÃH
Hz, o-C6H3Me2), 130.4 (dm, JCÃH
ꢀ
/
7Hz, ipso-C6H4Me), 130.3 (dm, JCÃH
ꢀ
/
159
159 Hz, o-
152 Hz, o-C6H4Me),
1
1
1
ꢀ
/
C6H3Me2), 129.87 (d, JCÃH
ꢀ/160Hz, p-C6H3Me2),
1
1
C6H3Me2), 133.2 (dm, JCÃH
ꢀ
/
130.09 (d, JCÃH
1JCÃH
160Hz, o-C6H3Me2), 130.27 (d, JCÃH
160Hz, o-C6H3Me2), 133.22 (d, JCÃH
ꢀ
/
160Hz, p-C6H3Me2), 130.17 (d,
1
136.6 (m, m-C6H3Me2), 136.7 (m, m-C6H3Me2), 136.8
(m, m-C6H4Me), 214.2 (CO). FABHRMS Calc. for
ꢀ
/
ꢀ
/
2
ꢀ
/
7.33 Hz; ipso-
79 56
2
[C44H43 Br Fe+ꢃ] ([MÃ
706.1903.
/
2CO+ꢃ]): 706.1898. Found:
C6H4F), 136.76 (q, JCÃH
ꢀ
/6Hz, m-C6H4Me2), 136.90
2
1
(q, JCÃH
Hz, m-C6H4F), 213.9 (s, CO). FABHRMS Calc. for
[C43H4079BrF56Fe].ꢃ ([MÃ2CO]+ꢃ): 710.1649. Found:
710.1646.
ꢀ
/
6Hz, m-C6H4Me2), 161.8 (dm, JCÃF
ꢀ245
/
3.3.4. 3b3 (1.17 g, 1.5 mmol, 75%)
/
IR (cmꢂ1, CH2Cl2) 1602 (Ph), 1991 (CO), 2034 (CO).
1H-NMR (300 MHz, CDCl3) 2.07 (s, 30 H, C6H3Me2),
6.70 (s, 10 H, o-C6H3Me2), 6.81 (s, 5 H, p-C6H3Me2).
3.3.7. 3b7 (1.18 g, 1.5 mmol, 75%)
IR (cmꢂ1, CH2Cl2) 1602 (Ph), 1996 (CO), 2037 (CO).
1H-NMR (300MHz, CDCl3) 2.06 (s, 12H, Me), 2.09 (s,
1
13C-NMR (75 MHz, CDCl3) 21.2 (qt, JCÃH
ꢀ
ꢀ
/
126 Hz,
4 Hz,
3
3JCÃH
ꢀ
/
4.5 Hz, C6H3Me2), 101.2 (t, JCÃH
/