1542 Organometallics, Vol. 15, No. 6, 1996
Song et al.
was stirred for 3 h at -78 °C. A 0.268 g amount (20%) of (µ-
- 2CO, 6.9), 444 (M+ - 3CO, 5.7), 416 (M+ - 4CO, 2.6), 388
(M+ - 5CO, 7.7), 360 (M+ - 6CO, 21.8), 176 (Fe2S2+, 46.8),
155 (MeC6H4SO2+, 6.7), 61 (EtS+, 5.4), 56 (Fe+, 8.6).
21
t-BuS)2Fe2(CO)6 and 0.105 g (9%) of 8c were obtained.
Com p ou n d 8d . The same SO2Cl2 procedure as that of 8a
was followed, but with use of [Et3NH][(µ-PhS)(µ-Se)Fe2(CO)6]
instead of [Et3NH][(µ-EtS)(µ-Se)Fe2(CO)6]. A 0.578 g amount
Com p ou n d s 9d a n d 10b. The same procedure as that for
preparation of 9c and 10a was followed, but [Et3NH][(µ-t-BuS)-
(µ-S)Fe2(CO)6] was used instead of [Et3NH][(µ-EtS)(µ-S)Fe2-
(CO)6]. The first red band gave 0.154 g (11%) of (µ-t-
BuS)2Fe2(CO)6.21 The second red band gave 0.043 (4%) of [(µ-
t-BuS)Fe2(CO)6]2(µ4-S)21 (9d ). The third red band gave 0.596
g (36%) of (µ-t-BuS)(µ-p-MeC6H4SO2S)Fe2(CO)6 (10b) as a
slightly air-sensitive red solid. 10b: mp 100-102 °C. Anal.
Calcd for C17H16Fe2O8S3: C, 36.71; H, 2.70. Found: C, 36.96;
H, 2.73. IR (KBr, disk): νCtO 2081.6 (s), 2040.8 (vs), 1999.6
33
(38%) of (µ-PhS)2Fe2(CO)6 and 0.230 g (18%) of [(µ-PhS)Fe2-
(CO)6]2(µ4-Se) (8d ) as a dark red solid were obtained. 8d : mp
146 °C dec. Anal. Calcd for C24H10Fe4O12S2Se: C, 33.64; H,
1.18. Found: C, 33.69; H, 1.30. IR (KBr, disk): νCtO 2081.6
(m), 2057.0 (s), 2032.4 (vs), 1991.4 (s), 1975.0 (s) cm-1
.
1H
NMR (CDCl3): δ 7.32 (s, 10H, 2C6H5) ppm. MS (EI, 80Se), m/z
(relative intensity): 802 (M+ - 2CO, 0.9), 746 (M+ - 4CO, 1.3),
718 (M+ - 5CO, 0.7), 690 (M+ - 6CO, 1.4), 662 (M+ - 7CO,
2.1), 634 (M+ - 8CO, 1.5), 606 (M+ - 9CO, 10.3), 578 (M+
-
(vs) cm-1; νSdO 1171.1 (m), 1089.1 (m) cm-1
.
1H NMR
10CO, 2.5), 550 (M+ - 11CO, 3.3), 522 (M+ - 12CO, 11.4),
445 (Fe4SeS2Ph+, 0.8), 368 (Fe4SeS2+, 100), 301 (Fe2SeSPh+,
6.0), 224 (Fe2SeS+, 11.2), 221 (Fe2SPh+, 14.5), 192 (Fe2Se+, 3.0),
144 (Fe2S+, 11.6), 77 (Ph+, 20.7), 56 (Fe+, 28.2).
(CDCl3): δ 1.60, 1.72 [s, s, 9H, C(CH3)3], 2.37 (s, 3H, p-CH3),
7.15, 7.24, 7.39, 7.48 (s, s, s, s, 4H, C6H4) ppm. MS (EI), m/z
(relative intensity): 496 (M+ - CO - S, 0.2), 492 (M+ - SO2,
0.3), 233 (Fe2S2Bu+, 3.7), 176 (Fe2S2+, 4.6), 91 (C6H4CH3+, 0.8),
57 (Bu+, 76.1), 56 (Fe+, 31.9).
However, when the reaction of [Et3NH][(µ-t-BuS)(µ-S)-
Fe2(CO)6] with p-MeC6H4SO2Cl was run at room temperature
for 2 h, 0.058 g (4%) of (µ-t-BuS)2Fe2(CO)6,21 0.710 g (66%) of
9d ,21 and 0.182 g (11%) of 10b were obtained.
Com p ou n d 8e. The same SO2Cl2 procedure as that of 8a
was followed, but with use of [Et3NH][(µ-PhSe)(µ-Se)Fe2(CO)6]
instead of [Et3NH][(µ-EtS)(µ-Se)Fe2(CO)6]. A 0.427 g amount
32
(24%) of (µ-PhSe)2Fe2(CO)6 and 0.165 g (12%) of [(µ-PhSe)-
Fe2(CO)6]2(µ4-Se) (8e) as a dark red solid were obtained. 8e:
mp 164 °C dec. Anal. Calcd for C24H10Fe4O12Se3: C, 30.32;
H, 1.06. Found: C, 30.33; H, 0.97. IR (KBr, disk): νCtO 2081.6
P r ep a r a tion of 8a -c,e,f a n d 11a -e by Rea ction of 6
w ith p-MeC6H4SO2Cl. To the solution of [Et3NH][(µ-EtS)-
(µ-Se)Fe2(CO)6] prepared above was added 1.144 g (6.0 mmol)
of toluene-4-sulfonyl chloride, and the stirring was continued
for 0.5 h at -78 °C and for 2 h at room temperature. After
the same workup as that for the preparation of 9c,d and 10a ,b,
the first red band gave 0.130 g (11%) of (µ-EtS)2Fe2(CO)621 and
the second red band gave 0.045 g (4%) of [(µ-EtS)Fe2(CO)6]2-
(µ4-Se) (8a ). The third red band gave 0.931 g (54%) of (µ-EtS)-
(µ-p-MeC6H4SO2)Fe2(CO)6 (11a ) as a red solid. 11a : mp 103-
104 °C. Anal. Calcd for C15H12Fe2O8S2: C, 36.32; H, 2.43.
Found: C, 36.05; H, 2.39. IR (KBr, disk): νCtO 2081.6 (s),
2048.8 (vs), 2016.0 (vs), 1966.8 (vs) cm-1; νSdO 1179.3 (s), 1089.1
(m), 2057.0 (s), 2032.4 (vs), 1991.4 (s), 1975.0 (s) cm-1
.
1H
NMR (CDCl3): δ 7.34 (s, 10H, 2C6H5) ppm. MS (EI, 80Se), m/z
(relative intensity): 702 (M+ - 9CO, 1.7), 618 (M+ - 12CO,
3.0), 464 (Fe4Se3+, 8.3), 461 (Fe4Se2Ph+, 100), 272 (Fe2Se2
,
+
25.4), 269 (Fe2SePh+, 15.5), 192 (Fe2Se+, 14.5), 77 (Ph+, 28.7),
56 (Fe+, 51.9).
P r ep a r a tion of 8e th r ou gh Rea ction w ith Su ccin oyl
Ch lor id e. To the solution of [Et3NH][(µ-PhSe)(µ-Se)Fe2(CO)6]
was added 0.16 mL (1.4 mmol) of succinoyl chloride, and the
reaction mixture was stirred for 3 h at -78 °C. A 0.486 g
32
amount (29%) of (µ-PhSe)2Fe2(CO)6 and 0.092 g (7%) of 8e
(m) cm-1 1H NMR (CDCl3): δ 1.62 (t, J ) 7.2 Hz, 3H, CH3),
.
were obtained.
2.24-2.76 (m, 5H, CH2, p-CH3), 7.12-7.64 (m, 4H, C6H4) ppm.
MS (EI), m/z (relative intensity): 300 (M+ - 6CO - C2H4, 0.1),
144 (Fe2S+, 3.0), 91 (MeC6H4+, 11.6), 56 (Fe+, 10.7).
Com p ou n d 8f. The same SO2Cl2 procedure as that of 8a
was followed, but with [Et3NH][(µ-p-MeC6H4Se)(µ-Se)Fe2(CO)6]
instead of [Et3NH][(µ-EtS)(µ-Se)Fe2(CO)6]. A 0.536 g amount
(29%) of (µ-p-MeC6H4Se)2Fe2(CO)6 and 0.195 g (13%) of [(µ-
p-MeC6H4Se)Fe2(CO)6]2(µ4-Se) (8f) as a dark red solid were
6
Com p ou n d s 8b a n d 11b. The same procedure as that for
8a and 11a was followed, but with use of [Et3NH][(µ-n-PrS)-
(µ-Se)Fe2(CO)6] instead of [Et3NH][(µ-EtS)(µ-Se)Fe2(CO)6]. The
first band gave 0.045 g (4%) of (µ-n-PrS)2Fe2(CO)6,21 the second
band gave 0.080 g (7%) of [(µ-n-PrS)Fe2(CO)6]2(µ4-Se) (8b), and
the third band gave 1.011 g (57%) of (µ-n-PrS)(µ-p-MeC6H4-
SO2)Fe2(CO)6 (11b) as a red solid. 11b: mp 66-68 °C. Anal.
Calcd for C16H14Fe2O8S2: C, 37.67; H, 2.77. Found: C, 37.56;
H, 2.87. IR (KBr, disk): νCtO 2081.6 (s), 2048.8 (vs), 1999.6
obtained. 8f: mp 163 °C dec. Anal. Calcd for C26H14Fe4O12
-
Se3: C, 31.91; H, 1.44. Found: C, 32.15; H, 1.19. IR (KBr,
disk): νCtO 2081.6 (m), 2051.6 (s), 2032.4 (vs), 1991.4 (vs) cm-1
.
1H NMR (CDCl3): δ 2.34 (s, 6H, 2CH3), 7.10, 7.19, 7.34, 7.44
(s, s, s, s, 8H, 2C6H4) ppm. MS (EI, 80Se), m/z (relative
intensity): 646 (M+ - 12CO, 0.5), 464 (Fe4Se3+, 1.2), 461 (Fe4-
+
Se2Ph+, 15.1), 272 (Fe2Se2+, 1.3), 192 (Fe2Se+, 1.0), 91 (MeC6H4
42.7), 56 (Fe+, 5.2).
,
(vs), 1966.8 (s) cm-1; νSdO 1179.3 (s), 1080.9 (m) cm-1 1H NMR
.
(CDCl3): δ 1.08 (t, J ) 7.2 Hz, 3H, CH3), 1.68-2.08 (m, 2H,
CH2), 2.16-2.76 (m, 5H, SCH2, p-CH3), 6.96-7.52 (m, 4H,
C6H4) ppm. MS (EI), m/z (relative intensity): 481 (M+ - CO,
P r ep a r a tion of 9c,d a n d 10a ,b by Rea ction of 4 (E )
S) w ith p-MeC6H4SO2Cl. To the solution of [Et3NH][(µ-EtS)-
(µ-S)Fe2(CO)6] prepared above was added 1.144 g (6.0 mmol)
of toluene-4-sulfonyl chloride, and the stirring was continued
for 0.5 h at -78 °C and for 2 h at room temperature. TLC
showed three main products. Solvent was removed under
vacuum to leave a red oily residue, which was purified by
column chromatography and TLC with petroleum ether and
1:1 (v/v) CH2Cl2/petroleum ether as eluant. The first red band
gave 0.075 g (6%) of (µ-EtS)2Fe2(CO)6.21 The second red band
gave 0.241 g (23%) of [(µ-EtS)Fe2(CO)6]2(µ4-S)3 (9c). The third
red band gave 0.408 g (26%) of (µ-EtS)(µ-p-MeC6H4SO2S)Fe2-
(CO)6 (10a ) as a slightly air-sensitive red solid. 10a : mp 94
°C dec. Anal. Calcd for C15H12Fe2O8S3: C, 34.11; H, 2.29.
Found: C, 33.79; H, 2.14. IR (KBr, disk): νCtO 2081.6 (s),
2040.6 (vs), 2007.8 (s), 1991.4 (vs) cm-1; νSdO 1138.3 (m), 1064.4
1.1), 454 (M+ - 2CO, 25.3), 426 (M+ - 3CO, 4.5), 398 (M+
-
4CO, 9.2), 370 (M+ - 5CO, 24.5), 342 (M+ - 6CO, 69.4), 300
(M+ - 6CO - C3H6, 100), 187 (Fe2SPr+, 1.6), 155 (MeC6H4-
SO2+, 9.7), 144 (Fe2S+, 57.5), 91 (MeC6H4+, 44.0), 56 (Fe+, 6.3),
43 (Pr+, 8.7).
Com p ou n d s 8c a n d 11c. The same procedure as that for
8a and 11a was followed, but with use of [Et3NH][(µ-t-BuS)-
(µ-Se)Fe2(CO)6] instead of [Et3NH][(µ-EtS)(µ-Se)Fe2(CO)6]. The
first red band gave 0.052 g (4%) of (µ-t-BuS)2Fe2(CO)6,21 the
second red band gave 0.114 g (9%) of [(µ-t-BuS)Fe2(CO)6]2(µ4-
Se) (8c), and the third red band gave 1.030 g (57%) of (µ-t-
BuS)(µ-p-MeC6H4SO2)Fe2(CO)6 (11c) as a red solid. 11c: mp
108-110 °C. Anal. Calcd for C17H16Fe2O8S2: C, 38.96; H,
3.08. Found: C, 38.84; H, 3.04. IR (KBr, disk): νCtO 2081.6
(s), 2048.8 (vs), 1999.6 (vs) cm-1; νSdO 1154.7 (s), 1089.1 (m)
(m) cm-1 1H NMR (CDCl3): δ 1.02, 1.44 (t, t, J ) 7.2 Hz, 3H,
.
CH3), 2.32-2.68 (m, 5H, CH2, p-CH3), 7.16-7.96 (m, 4H, C6H4)
cm-1 1H NMR (CDCl3): δ 1.58, 1.70 [s, s, 9H, C(CH3)3], 2.36,
.
ppm. MS (EI), m/z (relative intensity): 528 (M+, 0.3), 472 (M+
2.40 (s, s, 3H, p-CH3), 7.08-7.52 (m, 4H, C6H4) ppm. MS (EI),
m/z (relative intensity): 468 (M+ - 2CO, 1.9), 440 (M+ - 3CO,
(33) Nametkin, N. S.; Tyurin, V. D.; Kukina, M. A. J . Organomet.
Chem. 1978, 149, 355.
0.7), 412 (M+ - 4CO, 0.6), 384 (M - 5CO, 1.6), 356 (M+
-