218
R. Wang et al. / Journal of Organometallic Chemistry 658 (2002) 214Á227
/
(CH2Cl2)n(CO) 1945 (s), 1795 (vs, br) cmꢂ1; n(CN)
ꢂ
/
50 8C for 5 h, during which time the turbid red
solution gradually turned brownÁred. After vacuum
removal of the solvent, the brownÁred residue was
chromatographed on Al2O3 at ꢂ25 8C with petroleum
etherÁCH2Cl2 (5:1) as the eluant. A purpleÁred band
1
1993 cmꢂ1; H-NMR (CD3COCD3) d 7.56Á
/
7.26 (m,
/
5H, C6H5), 5.57 (s, 2H, C5H4), 5.47 (s, 2H, C5H4), 5.15
(s, 2H, C5H4), 5.02 (s, 2H, C5H4), 0.26 (s, 6H, SiCH3);
/
/
MS m/e 485 [Mꢁ], 382 [Mꢁꢂ
/
C6H5CN], 354 [Mꢁꢂ
/
/
/
C6H5CNꢂ
/
CO], 298 [Mꢁꢂ
Calc. for C22H19O3NSiFe2: C, 54.46; H, 3.95, N, 2.89.
/
C6H5CNꢂ3CO]. Anal.
/
was eluted and collected. The solvent was removed in
vacuo, and the crude product was recrystallized from
Found: C, 54.66, H, 4.02, N, 2.88%.
petroleum etherÁ
/
CH2Cl2 (5:1) solution at ꢂ
/
80 8C to
yield 0.082 g (37%, based on 1) of purpleÁ
/
red crystals of
1
23, which was identified by its m.p., and IR, H-NMR
and mass spectra.
2.15. Reaction of 1 with 7 to give [Fe2(m-CO){m-
C(H)C6H5}(CO)2{(h5-C5H4)2Si(CH3)2}] (23)
To a stirred, turbid red solution of 1 (0.400g, 0.494
2.18. Reaction of 2 with 8 to give 24
mmol) in 50 ml of THF at ꢂ
(0.581 mmol) of 7. The reaction mixture was stirred at
100 to ꢂ50 8C for 5 h, during which time the turbid
red solution gradually turned brown red. The resulting
solution was evaporated in vacuo at ꢂ40 8C to dryness,
and the dark-red residue was chromatographed on
Al2O3 at ꢂ25 8C with petroleum etherÁCH2Cl2 (5:1)
as the eluant. A purpleÁred band was eluted and
collected. The solvent was removed in vacuo, and the
residue was recrystallized from petroleum etherÁCH2Cl2
(5:1) solution at ꢂ80 8C to yield 0.120 g (51%, based on
1) of purpleÁred crystals of 23: m.p. (dec.) 228Á230 8C;
IR (CH2Cl2) n(CO) 1971 (vs), 1938 (s), 1775 (vs) cmꢂ1
1H-NMR (CD3COCD3) d 12.22 (s, 1H, m-CH), 7.37Á
/
100 8C was added 0.126 g
Compound 2 (0.389 g, 0.447 mmol) was reacted with
8 (0.340 g, 0.447 mmol) as described for the reaction of 1
with 8 to produce 0.090 g (38%, based on 2) of purpleÁ
red crystals of 24, which was identified by its m.p., IR,
1
and H-NMR and mass spectra.
ꢂ
/
/
/
/
/
/
/
2.19. Reaction of 3 with 8 to give [Fe2(m-CO){m-
C(H)C6H4CH3-p}(CO)2{(h5-C5H4)2Si(CH3)2}] (25)
/
/
/
/
As used in the reaction of 1 with 8, 0.313 g (0.380
mmol) of 3 was treated with 8 (0.289 g, 0.380 mmol) to
;
/
give 0.087 g (47%, based on 3) of 25 as purpleÁ
crystals: m.p. (dec.) 220Á222 8C; IR (CH2Cl2) n(CO)
1971 (s), 1939 (m), 1770 (m) cmꢂ1 1H-NMR
(CD3COCD3) d 12.23 (s, 1H, m-CH), 7.26Á6.93 (m,
/
red
7.01 (m, 5H, C6H5), 5.70 (s, 2H, C5H4), 5.62 (s, 2H,
C5H4), 5.35 (s, 2H, C5H4), 5.12 (s, 2H, C5H4), 0.58 (s,
3H, SiCH3), 0.35 (s, 3H, SiCH3); MS m/e 472 [Mꢁ], 444
/
;
/
[Mꢁꢂ
/
CO], 416 [Mꢁꢂ
/
2CO], 388 [Mꢁꢂ
/3CO]. Anal.
4H, C6H4CH3), 5.63 (s, 2H, C5H4), 5.57 (s, 2H, C5H4),
5.30 (s, 2H, C5H4), 5.26 (m, 3H, CH2Cl2), 5.09 (s, 2H,
C5H4), 2.23 (s, 3H, C6H4CH3), 0.59 (s, 3H, SiCH3), 0.34
Calc. for C22H20O3SiFe2: C, 55.96; H, 4.27. Found: C,
55.70; H, 4.28%.
(s, 3H, SiCH3); MS m/e 557 [Mꢁ], 529 [Mꢁꢂ
/
CO], 501
2.16. Reaction of 2 with 7 to give [Fe2(m-CO){m-
C(H)C6H4CF3-p}(CO)2{(h5-C5H4)2Si(CH3)2}] (24)
[Mꢁꢂ
/
2CO], 473 [Mꢁꢂ
/
3CO], 84 [CH2Cl2ꢁ]. Anal.
Calc. for C23H22O3SiFe2 1.5CH2Cl2: C, 47.95; H, 4.10.
Found: C, 47.77; H, 4.22%.
Similar to the reaction of 1 with 7, 2 (0.389 g, 0.447
mmol) was treated with 7 (0.112 g, 0.513 mmol) to
X-ray crystal structure determinations of complexes
14, 15, 22, and 23. The single crystals of 14, 15, 22, and
23 suitable for X-ray diffraction study were obtained by
afford 0.110 g (46%, based on 2) of purpleÁ
line 24: m.p. (dec.) 212Á214 8C; IR (CH2Cl2) n(CO)
1975 (s), 1944 (m), 1781 (m) cmꢂ1 1H-NMR
(CD3COCD3) d 12.04 (s, 1H, m-CH), 7.60Á7.36 (m,
/
red crystal-
/
recrystallization from petroleum etherÁ
/
CH2Cl2 solution
;
at ꢂ80 8C. Single crystals were mounted on a glass
/
/
fibre and sealed with epoxy glue. The X-ray diffraction
intensity data were collected with a Rigaku AFC7R or
Brock Smart diffractometer.
4H, C6H4CF3), 5.69 (s, 2H, C5H4), 5.60 (s, 2H, C5H4),
5.35 (s, 2H, C5H4), 5.25 (m, 1H, CH2Cl2), 5.12 (s, 2H,
C5H4), 0.59 (s, 3H, SiCH3), 0.36 (s, 3H, SiCH3); MS m/e
The structures of 14, 15, 22, and 23 were solved by
direct methods and expanded using Fourier techniques.
For 14, some non-hydrogen atoms were refined aniso-
tropically, while the rest were refined isotropically. For
15, 22, and 23, the non-hydrogen atoms were refined
anisotropically. For the four complexes the hydrogen
atoms were included but not refined. The final cycle of
full-matrix least-squares refinement gave agreement
512 [Mꢁꢂ
/
CO], 484 [Mꢁꢂ
/
2CO], 456 [Mꢁꢂ
3CO], 84
/
[CH2Cl2ꢁ]. Anal. Calc. for C23H19O3F3SiFe2 0.5CH2Cl2:
C, 48.47; H, 3.46. Found: C, 48.60; H, 4.00%.
2.17. Reaction of 1 with [(PPh3)2N][Cr(CO)4NO] (8)
to give 23
To a stirred solution of 1 (0.400 g, 0.494 mmol) in 50
factors of Rꢀ
and Rwꢀ0.062 for 15, Rꢀ
and Rꢀ0.0429 and Rwꢀ0.0514 for 23.
/
0.050 and Rwꢀ
/
0.062 for 14, Rꢀ
/
0.061
ml of THF at ꢂ
/
100 8C was added 0.340 g (0.494 mmol)
/
/
0.046 and Rwꢀ
/0.047 for 22,
of 8. The reaction mixture was stirred at ꢂ
/
100 to
/
/