28
L. Yang et al. / Journal of Organometallic Chemistry 585 (1999) 26–34
29.8 (CH), 22.5 (CH3). IR (CH2Cl2, cm−1): w(CN)=
2118. MS (m/z, rel. int.): 573 (M+1, 70%).
J=6.8 Hz, CH), 3.21 (s, 2 H, CC–H), 1.30–1.28 (d,
24 H, CH3). 13CNMR (CDCl3): l 186.5 (CO), 183.8
(CO), 150.4, 146.1, 127.5, 124.0, 82.8, 79.6, 30.0, 22.3.
IR (CH2Cl2, cm–1): w(CC–H)=3298 (m); w(CN)=
2179 (vw), 2146 (w); w(CO)=2039 (vs), 1992 (s), 1931
(s). FAB-MS (m/z, rel. int.): 729 (10%, M+1), 694
(85%, M–Cl+1), 673 (100%, M–2CO+1).
2.3. cis-W(4-CN-3,5-i-Pr2–C6H2CC-4-C5H4N)2(CO)4
(7)
7
2.5. Fe(p5-C5H5)Cl(4-CN-3,5-i-Pr2–C6H2CCSiMe3)2
(9)
W(CO)3(NCCH3)3 (55.0 mg, 0.138 mmol) is added
to a solution of 5 (70.0 mg, 0.243 mmol) in THF (7
ml). The solution is stirred at r.t. for about 18 h.
During this time the orange solution changes to red
brown. Then THF is removed under reduced pressure.
The solid residue is purified by chromotograpy on
silica gel using 5:1 ethyl acetate–n-hexane as the elu-
ent. The product is obtained as a brown–yellow solid
(40.8 mg, yield: 38.5%). The single crystal for the
X-ray crystallographic study was obtained by evapo-
rating a solution of 7 in acetone very slowly at r.t.
Found: C, 58.82; H, 4.62; N, 6.07. Calc. for
C44H40N4O4W.1.5 H2O, FW: 872.62+27.02 (899.65):
9
A solution of 3 (102 mg, 0.36 mmol) and Fe(h5-
C5H5)Cl(CO)2 (37 mg, 0.187 mmol) in THF (8 ml) is
stirred at r.t. for 40 h. The color of the solution
changed to brown. When the reaction is complete
(monitored by IR), the solvent is removed under re-
duced pressure. The solid residue is recrystallized from
dichloromethane–n-hexane. Two components are ob-
tained: A brown solid, 9, (20 mg, yield: 15%) and a
pale yellow solid, 18, (33 mg, yield: 26%), which is the
less soluble product. 9: Found: C, 67.72; H, 7.61; N,
3.91%. Calc. for C41H55N2Si2FeCl, FW: 723.32: C,
1
C, 58.74; H, 4.82; N, 6.23. H-NMR (CDCl3): l 8.63–
8.61 (m, 4 H, C5H4N), 7.40–7.39 (m, 4 H, C5H4N),
7.34 (s, 4 H, C6H2), 3.34–3.19 (m, 4 H, J=6.7 Hz,
CH), 1.33–1.31 (d, 24 H, J=6.9 Hz, CH3). 13C-NMR
(CDCl3): l 198.7 (CO), 196.0 (CO), 147.8, 146.2,
145.6, 145.5, 144.7, 143.8, 127.6, 127.4, 127.2, 126.6,
126.2, 121.6, 87.8, 87.6, 30.2, 29.9, 29.6, 22.6, 22.5,
22.1. IR (CH2Cl2, cm−1): w(CN)=2135 (m), 2073 (s);
w(CO)=2008(s), 1940 (sh), 1929 (vs). FAB-MS (m/z,
rel. int.): 873 (30%, M+1), 845 (32%, M–CO+1),
817 (38%, M–2CO+1), 289 (82%, L+1).
1
68.08; H, 7.66; N, 3.87%. H-NMR (CDCl3): l 7.26 (s,
4 H, C6H2), 4.76 (s, 5 H, C5H5), 3.50–3.40 (m, 4 H,
J=6.8 Hz, CH), 1.28–1.25 (d, 24 H, J=6.9 Hz,
CH3), 0.28 (s, 18 H, SiMe3). 13C-NMR (CDCl3): l
181.4 (CN), 144.9, 127.3, 127.1, 122.4, 104.8, 95.7,
81.1, 29.8, 22.6, 0.1. IR (CH2Cl2, cm−1): w(CN)=
2120 (s), 2073 (s). FAB-MS (m/z, rel. int.): 688 (20%,
M–Cl), 439 (15%, M–L), 404 (100%, M–L–Cl).
2.4. cis-ReCl(4-CN-3,5-i-Pr2–C6H2CCH)2(CO)3 (8)
2.6. Fe(p5-C5H5)Cl(4-CN-3,5-i-Pr2–C6H2CCH)2 (10)
10
8
ReCl(CO)5 (53.0 mg, 0.147 mmol) is dissolved in
THF (15 ml) and refluxed for 12 h (monitored by IR).
The resulting solution is then cooled to r.t., and 4
(62.0 mg, 0.294 mmol) is added. The mixture is stirred
at r.t. for 24 h (monitored by IR). After removing the
solvent, the solid residue is recrystallized from
dichloro-
methane–n-hexane. The product is obtained as a
brown–yellow solid (51.0 mg, 47.8%). Single crystals
suitable for X-ray crystallography were obtained by
evaporating a solution of 8 in CH2Cl2 slowly at r.t.
Found: C, 54.97; H, 5.08, N, 3.58%. Calc. for
C33H34N2O3ReCl.0·2 C6H14, FW: 728.27+17.23
(745.50): C, 55.10; H, 4.98; N, 3.76. 1H-NMR
(CDCl3): l 7.32 (s, 4 H, C6H2), 3.38–3.28 (m, 4 H,
The procedure described for 9 is followed. 4 (194
mg, 0.919 mmol), Fe(h5-C5H5)Cl(CO)2 (90 mg, 0.424
mmol), THF (20 ml), reaction time 16 h. Two prod-
ucts are obtained, a red solid, 10, (20 mg, yield: 8.2%)
and a deep brown solid, 19, (168 mg, yield: 69.5%),
which is the less soluble product. These two complexes
are purified by chromatography on silica gel using 2:1
ethyl acetate–n-hexane for 10 and methanol for 19 as
the eluents. 10: Found: C, 72.33; H, 6.59; N, 5.20%.
Calc. for C35H39N2FeCl, FW: 579.02: C, 72.63; H,
1
6.74; N, 4.84%. H-NMR (CDCl3): l 7.29 (s) and 7.26
(s) (4 H, C6H2), 4.76 (s, 5 H, C5H5), 3.6–3.3 (m, 4 H,
CH), 3.16 (s, 2 H, CC–H), 1.29–1.25 (d, 24 H, CH3).
13C-NMR (CDCl3): l 181.7 (CN), 145.0, 127.6, 127.3,
121.4, 83.4, 81.1, 78.4, 29.8, 22.6, 22.5. IR (CH2Cl2,