Inorganic Chemistry
Article
cally.38 The crystal of 9c was a partial merohedral twin. The twin law
was determined by PLATON39 to (1.001 0.000 0.003/0.000 −1.000
0.000/−0.333 0.000 −1.001). The contribution of the main
component was refined to 0.819(3). Crystallographic data as well as
structure solution and refinement details are summarized in Tables
S2−S4. XP (SIEMENS Analytical X-ray Instruments, Inc.) was used
for structure representations.
General Procedure for the Synthesis of [Fe2(CO)6{μ-S-
(CH2)nS}] (n = 4−8) (13−17). A solution of Fe3(CO)12 (200 mg,
0.40 mmol) and cyclic disulfide (6a−10a, 0.40 mmol) in THF (30
mL) was heated at reflux for 1 h under N2. The green solution turned
deep red, and the solvent was removed under reduced pressure. The
residue was purified by column chromatography using 100% hexane. A
red-orange fraction representing the complex (13−17, respectively)
was collected, and the solvent was removed in vacuo. The product was
obtained as a red-orange solid.
[Fe2(CO)6{μ-S(CH2)6S}]2 (18). Yield: 33% (0.13 mmol). Mp = 210−
211 °C. Anal. Calcd for C24H24Fe4O12S4: C, 33.67; H, 2.83; S, 14.98.
Found: C, 33.99; H, 3.10; S, 15.20. H NMR (400 MHz, CDCl3,
ppm): δ 2.46 (bs, 4H, e-SCH2), 2.13 (bs, 4H, a-SCH2), 1.62 (bs, 8H,
SCH2CH2), 1.48 (bs, 8H, SCH2CH2CH2). 13C{1H} NMR (100 MHz,
CDCl3, ppm): δ 208.97 (s, CO), 39.05 (s, e-SCH2), 32.68, 31.41,
28.76, 26.42, 23.84 (s, a-SCH2). IR (νCO, cm−1): 2068(m), 2033(vs),
1991(s). DEI-MS (m/z): 856 [M]+.
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[Fe2(CO)6{μ-S(CH2)7S}]2 (19). Yield: 25% (0.10 mmol). Mp = 102−
103 °C. Anal. Calcd for C26H28Fe4O12S4: C, 35.32; H, 3.19; S, 14.50.
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Found: C, 35.62; H, 3.38; S, 14.67. H NMR (400 MHz, CDCl3,
ppm): δ 2.47 (bs, 4H, e-SCH2), 2.08 (bs, 4H, a-SCH2), 1.75−1.59 (m,
8H, SCH2CH2), 1.46−1.26 (m, 12H, SCH2CH2(CH2)2). 13C{1H}
NMR (100 MHz, CDCl3, ppm): δ 208.97 (s, CO), 39.04 (s, e-SCH2),
32.68, 31.41, 28.76, 26.42, 23.84 (s, a-SCH2). IR (νCO, cm−1):
2068(m), 2033(vs), 1990(s). DEI-MS (m/z): 884 [M]+.
[Fe2(CO)6{μ-S(CH2)4S}] (13). Yield: 60% (0.24 mmol). Mp = 113−
[Fe2(CO)6{μ-S(CH2)8S}]2 (20). Yield: 30% (0.12 mmol). Mp = 165−
115 °C. Anal. Calcd for C10H8Fe2O6S2: C, 30.03; H, 2.02; S, 16.03.
166 °C. Anal. Calcd for C28H32Fe4O12S4: C, 36.87; H, 3.54; S, 14.06.
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Found: C, 30.40; H, 2.27; S, 16.20. H NMR (400 MHz, CDCl3,
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Found: C, 37.20; H, 3.65; S, 14.31. H NMR (400 MHz, CDCl3,
ppm): δ 2.59 (bs, 4H, SCH2), 1.66 (bs, 4H, SCH2CH2). 13C{1H}
NMR (100 MHz, CDCl3, ppm): δ 207.90 (s, CO), 33.80 (s, SCH2),
26.09 (s, SCH2CH2). IR (νCO, cm−1): 2072(m), 2033(vs), 1997(s).
DEI-MS (m/z): 400 [M]+.
ppm): δ 2.44 (bs, 4H, e-SCH2), 2.11 (bs, 4H, a-SCH2), 1.67 (bs, 8H,
SCH2CH2), 1.52 (bs, 8H, SCH2CH2CH2), 1.44 (bs, 4H, S-
(CH2)3CH2), 1.31 (bs, 4H, S(CH2)4CH2). 13C{1H} NMR (100
MHz, CDCl3, ppm): δ 209.04 (s, CO), 39.37 (s, e-SCH2), 32.96,
31.93, 29.12, 28.95, 28.42, 28.01, 24.64 (s, a-SCH2). IR (νCO, cm−1):
2068(m), 2032(vs), 1991(s). DEI-MS (m/z): 912 [M]+, 884 [M −
CO]+, 856 [M − 2CO]+, 828 [M − 3CO]+, 800 [M − 4CO]+, 772 [M
− 5CO]+, 744 [M − 6CO]+, 716 [M − 7CO]+, 688 [M − 8CO]+, 660
[M − 9CO]+, 632 [M − 10CO]+, 604 [M − 11CO]+, 576 [M −
12CO]+.
General Procedure for the Synthesis of Complexes 21−23
via Reaction of Compounds 8b−10b with Fe3(CO)12 in a 1:1
Molar Ratio. A solution of Fe3(CO)12 (100 mg, 0.20 mmol) and
cyclic tetrasulfide (8b-10b, 0.20 mmol) in THF (40 mL) was heated at
reflux for 2 h under N2. The green solution turned deep red, and the
solvent was removed under reduced pressure. The residue was purified
by column chromatography using 100% hexane. A yellow-orange
fraction representing the complex (21−23, respectively) was collected,
and the solvent was removed in vacuo. The product was obtained as a
red-orange solid.
[Fe2(CO)6{μ-S(CH2)5S}] (14). Yield: 55% (0.22 mmol). Mp = 116−
118 °C. Anal. Calcd for C11H10Fe2O6S2: C, 31.91; H, 2.43; S, 15.49.
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Found: C, 32.31; H, 2.61; S, 15.79. H NMR (400 MHz, CDCl3,
ppm): δ 2.61 (t, 4H, SCH2), 1.75 (p, 4H, SCH2CH2), 1.56 (p, 2H,
SCH2CH2CH2). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 207.72
(s, CO), 30.21 (s, SCH2), 29.37 (s, SCH2CH2) 28.64 (s,
SCH2CH2CH2). IR (νCO, cm−1): 2072(m), 2033(vs), 1999(s). DEI-
MS (m/z): 414 [M]+.
[Fe2(CO)6{μ-S(CH2)6S}] (15). Yield: 53% (0.21 mmol). Mp = 119−
121 °C. Anal. Calcd for C12H12Fe2O6S2: C, 33.67; H, 2.83; S, 14.98.
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Found: C, 33.96; H, 3.14; S, 15.12. H NMR (400 MHz, CDCl3,
ppm): δ 2.49 (t, 4H, SCH2), 1.64 (bs, 4H, SCH2CH2), 1.53 (bs, 4H,
SCH2CH2CH2). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 207.68
(s, CO), 32.08 (s, SCH2), 30.52 (s, SCH2CH2) 26.01 (s,
SCH2CH2CH2). IR (νCO, cm−1): 2072(m), 2033(vs), 1998(s). DEI-
MS (m/z): 428 [M]+.
[Fe2(CO)6{μ-S(CH2)7S}] (16). Yield: 48% (0.19 mmol). Mp = 94−96
[Fe2(CO)6{(μ-S(CH2)6S)2}] (21). Yield: 15% (0.030 mmol). Mp =
170−171 °C. Anal. Calcd for C18H24Fe2O6S4: C, 37.51; H, 4.20; S,
22.25. Found: C, 37.26; H, 4.03; S, 21.96. 1H NMR (400 MHz,
CDCl3, ppm): δ 2.71 (bs, 4H, SSCH2), 2.51 (bs, 2H, e-SCH2), 2.14
(bs, 2H, a-SCH2), 1.72 (bs, 4H, SSCH2CH2), 1.43 (bs, 4H,
SCH2CH2), 1.27 (bs, 8H, S(CH2)2(CH2)2). IR (νCO, cm−1):
2069(m), 2031(vs), 1992(s). DEI-MS (m/z): 576 [M]+.
°C. Anal. Calcd for C13H14Fe2O6S2: C, 35.32; H, 3.19; S, 14.50.
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Found: C, 35.72; H, 3.30; S, 14.70. H NMR (400 MHz, CDCl3,
ppm): δ 2.30 (bs, 4H, SCH2), 1.60 (bs, 4H, SCH2CH2), 1.48 (bs, 4H,
SCH2CH2CH2), 1.38 (bs, 2H, SCH2CH2CH2CH2) . 13C{1H} NMR
(100 MHz, CDCl3, ppm): δ 207.70 (s, CO), 31.83 (s, SCH2), 29.40 (s,
SCH2CH2) 27.54 (s, SCH2CH2CH2), 25.81 (s, SCH2CH2CH2CH2).
IR (νCO, cm−1): 2072(m), 2033(vs), 1994(s). DEI-MS (m/z): 442
[M]+.
[Fe2(CO)6{(μ-S(CH2)7S)2}] (22). Yield: 10% (0.020 mmol). Mp =
73−75 °C. Anal. Calcd for C20H28Fe2O6S4: C, 39.75; H, 4.67; S, 21.22.
[Fe2(CO)6{μ-S(CH2)8S}] (17). Yield: 48% (0.19 mmol). Mp = 83−85
1
Found: C, 39.95; H, 4.48; S, 21.46. H NMR (400 MHz, CDCl3,
°C. Anal. Calcd for C14H16Fe2O6S2: C, 36.87; H, 3.54; S, 14.06.
1
ppm): δ 2.75 (bs, 4H, SSCH2), 2.50 (bs, 2H, e-SCH2), 2.11 (bs, 2H, a-
SCH2), 1.73 (bs, 4H, SSCH2CH2), 1.46 (bs, 4H, SCH2CH2), 1.33−
1.29 (m, 12H, S(CH2)2(CH2)2). IR (νCO, cm−1): 2069(m), 2032(vs),
1991(s). DEI-MS (m/z): 604 [M]+.
[Fe2(CO)6{(μ-S(CH2)8S)2}] (23). Yield: 12% (0.024 mmol). Mp =
122−123 °C. Anal. Calcd for C22H32Fe2O6S4: C, 41.78; H, 5.10; S,
20.28. Found: C, 41.48; H, 5.32; S, 19.99. 1H NMR (400 MHz,
CDCl3, ppm): δ 2.72 (bs, 4H, SSCH2), 2.52 (bs, 2H, e-SCH2), 2.15
(bs, 2H, a-SCH2), 1.70 (bs, 4H, SSCH2CH2), 1.45 (bs, 4H,
SCH2CH2), 1.40 (bs, 8H, SCH2CH2CH2), 1.39 (bs, 4H, S-
(CH2)3CH2), 1.30 (bs, 4H, S(CH2)4CH2). IR (νCO, cm−1):
2069(m), 2030(vs), 1991(s). DEI-MS (m/z): 632 [M]+.
Found: C, 37.13; H, 3.49; S, 14.33. H NMR (400 MHz, CDCl3,
ppm): δ 2.45 (bs, 2H, e-SCH2), 2.18 (bs, 2H, a-SCH2), 1.87 (bs, 2H,
e-SCH2CH2), 1.63 (bs, 2H, SCH2CH2CH2) 1.54 (bs, 2H, a-
SCH2CH2), 1.44 (bs, 2H, SCH2CH2CH2CH2), 1.34 (bs, 2H,
S(CH2)4CH2). 13C{1H} NMR (100 MHz, CDCl3, ppm): δ 209.17
(s, CO), 37.36 (s, e-SCH2), 30.46 (s, e-SCH2CH2) 29.84 (s,
SCH2CH2CH2), 28.28 (s, SCH2CH2CH2CH2), 27.26 (s, S-
(CH2)4CH2), 26.82 (s, S(CH2)5CH2), 24.77 (s, a-SCH2CH2), 23.42
(s, a-SCH2). IR (νCO, cm−1): 2069(m), 2030(vs), 1992(s). DEI-MS
(m/z): 456 [M]+.
General Procedure for the Synthesis of Complexes 18−20
via Reaction of Compounds 8b−10b with Fe3(CO)12 in a 1:2
Molar Ratio. A solution of Fe3(CO)12 (400 mg, 0.80 mmol) and
cyclic tetrasulfide (8b−10b, 0.40 mmol) in THF (40 mL) was heated
at reflux for 2 h under N2. The green solution turned deep red, and the
solvent was removed under reduced pressure. The residue was purified
by column chromatography using 100% hexane. A red-orange fraction
representing the complex (18−20, respectively) was collected, and the
solvent was removed in vacuo. The product was obtained as a red-
orange solid.
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Inorg. Chem. XXXX, XXX, XXX−XXX