3500 Organometallics, Vol. 19, No. 18, 2000
Liu et al.
g, 0.632 mmol) and BBr3 (0.30 mL, 3.20 mmol). A brown-red
preparation of 5 gave 0.097 g (51%, based on 3) of blackish
red crystals of 9: mp 70-72 °C dec; IR (CH2Cl2) ν(CO) 1994
solid product, 4, was obtained, yield 0.36 g (75%), mp 76-78
°C dec; IR (CH2Cl2) ν(CO) 2035 (vs), 2005 (m), 1844(s) cm-1
;
(vs), 1898 (m), 1781 (m) cm-1; H NMR (CD3COCD3) δ 8.30-
1
1H NMR (CD3COCD3) δ 8.40 (m, 2H, C6H5), 7.73 (m, 1H, C6H5),
7.36 (m, 1H, C6H5), 5.82 (s, 10H, C5H5), 3.48 (q, 2H,
(CH3CH2)2O), 2.85 (s, 3H, C6H4CH3), 1.14 (t, 3H, (CH3CH2)2O).
Anal. Calcd for C21H22O3BBr4Fe2‚0.5(C2H5)2O: C, 34.68; H,
2.78. Found: C, 35.01; H, 2.96.
6.94 (m, 9H, C6H5 + C6H4NO2), 5.43 (s, 10H, C5H5); MS m/e
254 (M+ - 3CO - Ph - SC6H4NO2), 275 [C5H5FeSC6H4NO2]+.
Anal. Calcd for C26H19O5NSFe2: C, 54.86; H, 3.36; N, 2.46.
Found: C, 55.01; H, 3.51; N, 2.11.
Rea ction of 4 w ith Na SP h To Give [F e2(µ-CO){µ-
C(SP h )C6H4Me-p }(CO)2(η-C5H5)2] (10). To 0.240 g (0.316
mmol) of freshly prepared 4 dissolved in 50 mL of THF at
-80 °C was added 0.043 g (0.324 mmol) of NaSPh. The
reaction mixture was stirred at -80 to -40 °C for 4-5 h,
during which time the turbid solution turned clear purple-
red gradually. Further treatment as described in the reaction
of 3 with NaSMe afforded 0.122 g (72%, based on 4) of purple-
red crystals of 10: mp 92-93 °C dec; IR (CH2Cl2) ν(CO) 1983
Rea ction of 3 w ith Na SMe To Give [F e2(µ-CO){µ-
C(SMe)P h }(CO)2(η-C5H5)2] (5). To 0.250 g (0.335 mmol) of
freshly prepared (in situ) 3 dissolved in 50 mL of THF at -80
°C was added 0.024 g (0.342 mmol) of NaSMe. The reaction
mixture was stirred at -80 to -60 °C for 1 h, during which
time the turbid solution turned clear deep red gradually. After
stirring at -60 to -20 °C for an additional 3 h, the resulting
solution was evaporated under high vacuum at -35 °C to
dryness and the dark red residue was chromatographed on
an alumina column (1.6 × 15-20 cm) at -25 °C with
petroleum ether/CH2Cl2 (5:1) as the eluant. The purple-red
band was eluted and collected. After vacuum removal of the
solvent, the residue was recrystallized from petroleum ether/
CH2Cl2 (15:1) solution at -80 °C to give 0.087 g (56%, based
on 3) of purple-red crystals of 5: mp 147-148 °C dec; IR
1
(vs), 1945 (m), 1780 (s) cm-1; H NMR (CD3COCD3) δ 7.42-
6.34 (m, 9H, C6H5 + C6H4CH3), 5.22 (s, 10H, C5H5), 2.11 (m,
3H, CH3C6H4); MS m/e 254 (M+ - 3CO - MeC6H4 - SPh),
230 [C5H5FeSPh]+. Anal. Calcd for C27H22O3SFe2: C, 60.26;
H, 4.12. Found: C, 60.10; H, 4.03.
Rea ction of 4 w ith Na SC6H4Me-p To Give [F e2(µ-CO)-
{µ-C(SC6H4Me-p )C6H4Me-p }(CO)2(η-C5H5)2] (11). Similar to
the reaction of 4 with NaSPh, 0.240 g (0.316 mmol) of 4 reacted
with 0.048 g (0.327 mmol) of NaSC6H4Me-p at -80 to -40 °C
for 4-5 h. Further treatment as described for the preparation
of 10 yielded 0.131 g (75%, based on 4) of 11 as purple-red
crystals: mp 116-118 °C dec; IR (CH2Cl2) ν(CO) 1984 (s), 1942
(m), 1786 (s) cm-1; 1H NMR (CD3COCD3) δ 7.38-6.34 (m, 2H,
2C6H4CH3), 7.02 (m, 4H, 2C6H4CH3), 6.71 (m, 2H, 2C6H4CH3),
5.17 (s, 10H, C5H5), 2.24 (s, 3H, CH3C6H4S), 2.14 (s, 3H,
CH3C6H4); MS m/e 254 (M+ - 3CO - MeC6H4 - SC6H4Me),
244 [C5H5FeSC6H4Me]+. Anal. Calcd for C28H24O3SFe2: C,
60.90; H, 4.38. Found: C, 60.83; H, 4.40.
(CH2Cl2) ν(CO) 1983 (vs), 1939 (vs), 1756(s) cm-1 1H NMR
;
(CD3COCD3) δ 7.62-6.95 (m, 5H, C6H5), 5.13 (s, 10H, C5H5),
2.28 (s, 3H, CH3); MS m/e 254 (M+ - 3CO - Ph - SMe), 168
[C5H5FeSMe]+. Anal. Calcd for C21H18O3SFe2: C, 54.59; H,
3.93. Found: C, 54.44; H, 3.77.
Rea ction of 3 w ith Na SEt To Give [F e2(µ-CO){µ-
C(SEt)P h }(CO)2(η-C5H5)2] (6). Similar to the procedures for
the reaction of 3 with NaSMe, compound 3 (0.250 g, 0.335
mmol) was treated with NaSEt (0.029 g, 0.344 mmol) at -80
to -20 °C for 4 h, during which time the turbid solution turned
clear deep red gradually. Further treatment of the resulting
mixture as described above gave 0.099 g (62%, based on 3)
of dark reddish red crystals of 6: mp 138-140 °C dec; IR
Rea ction of 3 w ith Na OP h To Give [F e2(µ-CO){µ-
C(OP h )P h }(CO)2(η-C5H5)2] (12). Compound 3 (0.250 g, 0.335
mmol) was treated, in a manner similar to that for the reaction
of 3 with NaSMe, with NaOPh (0.040 g, 0.343 mmol) at -80
to -20 °C for 4 h, during which time the turbid solution turned
dark brown-red gradually. Further treatment of the resulting
mixture as described in the reaction of 3 with NaSMe afforded
0.065 g (38%, based on 3) of brown-red crystalline 12: mp
62-64 °C dec; IR (CH2Cl2) ν(CO) 2010 (vs), 1977 (s), 1813 (m)
cm-1; 1H NMR (CD3COCD3) δ 8.43 (m, 3H, C6H5), 7.74 (m, 4H,
C6H5), 7.40 (m, 3H, C6H5), 5.26 (s, 10H, C5H5); MS m/e 254
(M+ - 3CO - Ph - OPh), 186 [(C5H5)2Fe]+. Anal. Calcd for
(CH2Cl2) ν(CO) 1983 (vs), 1943 (m), 1774(s) cm-1 1H NMR
;
(CD3COCD3) δ 7.65-6.94 (m, 5H, C6H5), 5.28 (m, 1H,
CH2Cl2), 5.12 (s, 10H, C5H5), 2.47 (q, 2H, CH2CH3), 0.94 (t,
3H, CH2CH3); MS m/e 254 (M+ - 3CO - Ph - SEt), 182
[C5H5FeSEt]+, 84 (CH2Cl2). Anal. Calcd for C22H20O3SFe2‚
0.5CH2Cl2: C, 52.07; H, 4.08. Found: C, 52.26; H, 3.99.
Rea ction of 3 w ith Na SP h To Give [F e2(µ-CO){µ-
C(SP h )P h }(CO)2(η-C5H5)2] (7). Compound 3 (0.250 g, 0.335
mmol) was treated, in a manner similar to that in the reaction
of 3 with NaSMe, with 0.045 g (0.339 mmol) of NaSPh at -80
to -20 °C for 4-5 h. Further treatment of the resulting dark
red solution as described for the reaction of 3 with NaSMe
afforded 0.123 g (70%, based on 3) of 7 as red crystals: mp
107-108 °C dec; IR (CH2Cl2) ν(CO) 1985 (vs), 1946 (s),
C
26H20O4Fe2: C, 57.80; H, 3.84. Found: C, 57.66; H, 3.53.
Rea ction of 3 w ith Na N(SiMe3)2 To Give [F e2(µ-CO)-
{µ-C(N(SiMe3)2)P h }(CO)2(η-C5H5)2] (13). As described for
the reaction of 3 with NaSMe, compound 3 (0.250 g, 0.335
mmol) was treated with NaN(SiMe3)2 (0.062 g, 0.338 mmol)
at -80 to -20 °C for 5 h, during which time the turbid solution
turned blackish red gradually. Further treatment of the
resulting mixture as described for the preparation of 5 gave
0.063 g (31%, based on 3) of blackish red crystals of 13: mp
50 °C dec; IR (CH2Cl2) ν(CO) 1996(s), 1969 (s), 1786 (w)
1780(s) cm-1 1H NMR (CD3COCD3) δ 8.06-6.76 (m, 10H,
;
C6H5), 5.26 (s, 10H, C5H5); MS m/e 254 (M+ - 3CO - Ph -
SPh), 230 [C5H5FeSPh]+. Anal. Calcd for C26H20O3SFe2: C,
59.57; H, 3.85. Found: C, 59.46; H, 3.74.
Rea ction of 3 w ith Na SC6H4Me-p To Give [F e2(µ-CO)-
{µ-C(SC6H4Me-p )P h }(CO)2(η-C5H5)2] (8). Similar to that for
the reaction of 3 with NaSMe, 3 (0.250 g, 0.335 mmol) was
treated with 0.050 g (0.340 mmol) of NaSC6H4Me-p at -80 to
-20 °C for 4-5 h. Further treatment of the resulting mixture
as described for the preparation of 5 yielded 0.134 g (74%,
based on 3) of purple-red crystalline 8: mp 100-101 °C dec;
IR (CH2Cl2) ν(CO) 1984 (vs), 1945 (s), 1772 (vs) cm-1; 1H NMR
(CD3COCD3) δ 7.48-6.75 (m, 9H, C6H5 +C6H4CH3), 5.22 (s,
10H, C5H5), 2.21 (s, 3H, C6H4CH3); MS m/e 254 (M+ - 3CO -
Ph - SC6H4Me), 244 [C5H5FeSC6H4Me]+. Anal. Calcd for
cm-1 1H NMR (CD3COCD3) δ 7.80-6.97 (m, 5H, C6H5),
;
5.11 (s, 10H, C5H5), 0.89 (s, 18H, CH3); MS m/e 254 [M+
-
3CO - Ph - N(SiMe3)2], 186 [(C5H5)2Fe]+. Anal. Calcd for
C26H33O3NSi2Fe2: C, 54.27; H, 5.78; N, 2.44. Found: C, 54.13;
H, 5.92; N, 2.59.
Rea ction of 3 w ith [Et3NH][F e2(µ-CO)(µ-SBu n )(CO)6]
To Give [F e2(µ-CO){µ-C(SH)P h }(CO)2(η-C5H5)2] (14). To a
solution of 0.338 g (0.671 mmol) of Fe3(CO)12 in 50 mL of THF
was added 0.072 mL (0.676 mmol) of n-BuSH and 0.094 mL
(0.672 mmol) of Et3N with stirring. The mixture was stirred
at room temperature for 40 min. The resulting brown-red
solution of [Et3NH][Fe2(µ-CO)(µ-SBun)(CO)6]17 was cooled to
-80 °C and then was poured rapidly into 0.50 g (0.671 mmol)
of freshly prepared 3 previously cooled to a -80 °C. The
mixture was stirred at -80 to -40 °C for 6 h, during which
C
27H22O3SFe2: C, 60.22; H, 4.12. Found: C, 59.86; H, 4.02.
Rea ction of 3 w ith Na SC6H4NO2-p To Give [F e2(µ-CO)-
{µ-C(SC6H4NO2-p )-P h }(CO)2(η-C5H5)2] (9). The reaction of
3 (0.250 g, 0.335 mmol) with NaSC6H4NO2-p (0.060 g, 0.338
mmol) was as described in the reaction of 3 with NaSMe at
-80 to -20 °C for 5 h. Further treatment as described for the