K. Ma et al. / Journal of Organometallic Chemistry 664 (2002) 94ꢀ
/105
103
3
ml). The resulting deep red mixture was allowed to
warm to ambient temperature and stirred for 1 h,
whereupon a pale yellow precipitate formed, which
was removed by filtration. The filtrate was evaporated
to a volume of about 20 ml in vacuo and stored at
C5H4), 5.30 (s, 2H, NH), 6.50 (dd, 2H, J(H,H)ꢂ
/
8.8
5
Hz, J(H,H)ꢂ
(2ꢅdd, 2ꢅ
Ph-2,3,5,6), 6.82 (dd, 2H, 3J(H,H)ꢂ
2.2 Hz, Phꢁ-2,6 or Phꢁ-3,5). 13C-NMR (62.9 MHz,
CDCl3): d 55.3 (OCH3ꢁ); 55.4 (OCH3), 68.3 (C5H5), 70.1,
/
2.2 Hz, Phꢁ-2,6 or Phꢁ-3,5), 6.55, 6.67
3
5
/
/
4H, J(H,H)ꢂ
/
8.9 Hz, J(H,H)ꢂ
/2.3 Hz,
/
8.8 Hz, 5J(H,H)ꢂ
/
ꢄ30 8C for 72 h. Compound 4, which precipitated as
/
/
orange crystalline solid, was isolated by filtration,
triturated with pentane (10 ml) and dried in vacuo.
Yield: 2.56 g (90%).
73.6 (C5H4), n.o. (C5H4-ipso), 113.3 (Phꢁ-2,6 or Phꢁ-
3,5) 113.5, 123.9 (Ph-2,3,5,6), 128.1 (Phꢁ-2,6 or Phꢁ-3,5),
136.4 (CÃ
O). ESI-MS: m/z 757 [Mꢃ]. Anal. Calc. for
C41H41B2Fe2N3O3ꢅ0.4C7H8: C, 66.26; H, 5.61; N,
/
N), 140.9 (CꢁÃ
/
N), 154.8 (CÃ
/
O), 155.2 (CꢁÃ
/
11B-NMR (128.4 MHz, C6D6): d 45.7 (h1/2
ꢂ
/
140 Hz).
1H-NMR (250.1 MHz, CDCl3): d 0.15 (s, 9H, SiMe3),
1.62 (s, 9H, CMe3), 4.19 (s, 5H, C5H5), 4.43, 4.52 (2ꢅ
/
/
5.29. Found: C, 66.10; H, 5.64; N, 5.25%.
3
vtr, 2ꢅ
/
2H, J(H,H)ꢂ4
/
J(H,H)ꢂ
1.8 Hz, C5H4). 13C-
/
NMR (62.9 MHz, CDCl3): d 5.7 (SiMe3), 33.0 (CMe3),
56.8 (CMe3), 69.5 (C5H5), 72.5, 75.0 (C5H4) n.o. (C5H4-
ipso).
4.7. Preparation of 7
4.7.1. Method 1
Compound 1 (0.33 g, 0.93 mmol) in C6H5CH3 (20 ml)
was added with stirring at ꢄ78 8C to 6 (0.70 g, 0.92
4.5. Preparation of 5
/
mmol) and Et3N (0.19 g, 1.88 ml) in C6H5CH3 (40 ml).
The mixture was allowed to warm to ambient tempera-
ture and then heated under reflux for 2 h, whereupon its
color changed gradually from red to orange, and a pale
yellow precipitate formed. After filtration, the volume of
the filtrate was reduced to about 10 ml. Compound 7,
which crystallized as orange solid upon storage of the
Sodium bis(trimethylsilyl)amide (0.17 g, 0.93 mmol)
in C6H5CH3 was slowly added with stirring at ꢄ78 8C
/
to a solution of 1 in C7H16 (0.66 g, 1.85 mmol). After the
mixture had been allowed to warm to ambient tempera-
ture, NaBr was removed by filtration. X-ray quality
crystals of 5 grew from the filtrate at ambient tempera-
ture over a period of several days. Yield: 0.49 g (83%).
29Si{1H}-NMR (49.7 MHz, C6D6): d 5.91 (s, SiMe3).
1H-NMR (250.1 MHz, C6D6): d 0.26 (s, 9H, SiMe3),
filtrate at ꢄ30 8C for 12 h, was isolated by filtration,
/
triturated with C5H12 (5 ml) and dried in vacuo. Yield:
0.60 g (69%). Orange X-ray quality crystals of 7 were
obtained from its C6H6 solution at ambient tempera-
ture.
4.04 (s, 10H, C5H5), 4.24, 4.53 (2ꢅ
/
vtr, 2ꢅ
/
4H,
3J(H,H)ꢂ4 1.8 Hz, C5H4). 13C-NMR (62.9
/
J(H,H)ꢂ
/
MHz, C6D6): d 5.7 (SiMe3), 69.8 (C5H5), 74.6, 76.6
(C5H4), n.o. (C5H4-ipso).
4.7.2. Method 2
Compound 6 (0.75 g, 0.99 mmol) in C6H5CH3 (30 ml)
was treated with n-BuLi (0.13 g, 2.03 mmol) in C6H14
4.6. Preparation of 6
A mixture of 4-methoxyaniline (0.89 g, 7.23 mmol)
and Et3N (1.47 g, 14.53 mmol) in C6H5CH3 (30 ml) was
(1.2 ml) and stirred for 0.5 h at ꢄ
mmol) in C6H5CH3 (20 ml) was added at ꢄ
/
78 8C. 1 (0.35 g, 0.98
78 8C, the
/
added dropwise with stirring at ꢄ
/
78 8C to a solution of
orange slurry was allowed to warm to ambient tem-
perature and stirred for 2 h. After filtration, the volume
of the filtrate was reduced to about 10 ml. Compound 7,
which was obtained as an orange crystalline solid upon
1 (2.58 g, 7.25 mmol) in C6H5CH3 (40 ml). The color of
the reaction mixture changed gradually from red to
yellow, and a pale yellow precipitate formed upon
warming to ambient temperature. The resulting slurry
was stirred at ambient temperature for 24 h. After
filtration, the volume of the filtrate was reduced to
about 20 ml in vacuo. Compound 6, which crystallized
as an orange solid upon storage of the C6H5CH3
storage of the solution at ꢄ30 8C for 12 h, was isolated
/
by filtration, triturated with C5H12 (5 ml) and dried in
vacuo.Yield: 0.68 g (73%).
11B-NMR (128.4 MHz, CDCl3): d 35.1 (h1/2
Hz). H-NMR (250.1 MHz, CDCl3): d 2.87 (vtr, 6H,
ꢂ1700
/
1
solution at ꢄ
/
30 8C for 72 h, was isolated by filtration,
3J(H,H)ꢂ4
OCH3), 4.00 (vtr, 6H, 3J(H,H)ꢂ4
C5H4), 4.06 (s, 15H, C5H5), 6.90, 7.21 (2ꢅ
3J(H,H)ꢂ8.8 Hz, 5J(H,H)ꢂ
2.3 Hz, 2ꢅ6H, Ph-
2,3,5,6). 13C-NMR (62.9 MHz, CDCl3):
55.4
(OCH3), 68.6 (C5H5), 70.2, 77.0 (C5H4), n.o. (C5H4-
/
J(H,H)ꢂ
/
1.8 Hz, C5H4), 3.90 (s, 9H,
J(H,H)ꢂ1.8 Hz,
dd,
triturated with C5H12 (10 ml) and dried in vacuo. Yield:
1.40 g (77%). Orange X-ray quality crystals of 6 were
obtained from its C6H6 solution at ambient tempera-
ture.
11B-NMR (128.4 MHz, CDCl3): d 35.3 (h1/2
Hz). 1H-NMR (250.1 MHz, CDCl3): d 3.61 (s, 3H,
/
/
/
/
/
/
d
ꢂ1400
/
ipso), 113.1, 131.6 (Ph-2,3,4,5), 141.1 (CÃ
/
N), 157.3 (CÃ
/
OCH3ꢁ); 3.66 (s, 6H, OCH3), 4.00 (vtr, 4H,
O). ESI-MS: m/z 951 [Mꢃ]. Anal. Calc. for
C51H48B3Fe3N3O3: C, 64.42; H, 5.09; N, 4.42. Found:
C, 64.29; H, 5.47; N, 4.47%.
3J(H,H)ꢂ4
/
J(H,H)ꢂ
/
1.8 Hz, C5H4), 4.02 (s, 10H,
J(H,H)ꢂ1.8 Hz,
C5H5), 4.10 (vtr, 4H, 3J(H,H)ꢂ4
/
/
Ma, Kuangbiao
