Reactions of [(μ-RS)(μ-S){Fe2(CO)6}2(μ 4-S)]- with acid chlorides and diacid chlorides. Crystal structure of (μ-PhCH2S)[μ-CH2=C(Me)COS][Fe2(CO) 6]2</su

Article abstract of DOI:10.1016/S0022-328X(00)00042-5

The reaction of anionic complexes [(μ-RS)(μ-S){Fe₂(CO)₆}₂(μ ₄-S)]^- (1) with acid chlorides R¹COCl [R¹=Me, Ph, PhCH=CH, CH₂=C(Me)] gives S-acylated compounds (μ-RS)(μ-R

Full text of DOI:10.1016/S0022-328X(00)00042-5

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 601 (2000) 108–113
Reactions of [(m-RS)(m-S){Fe2(CO)6}2(m4-S)]− with acid chlorides
and diacid chlorides. Crystal structure of
(m-PhCH2S)[m-CH2ꢀC(Me)COS][Fe2(CO)6]2(m4-S)
Zhong-Xia Wang a,*, Cheng-Sheng Jia a, Zhong-Yuan Zhou b, Xiang-Ge Zhou b
a Department of Chemistry, Uni6ersity of Science and Technology of China, Hefei, Anhui 230026, People’s Republic of China
b Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, People’s Republic of China
Received 12 November 1999; accepted 5 January 2000
Abstract
The reaction of anionic complexes [(m-RS)(m-S){Fe2(CO)6}2(m4-S)]− (1) with acid chlorides R1COCl [R1=Me, Ph, PhCHꢀCH,
CH2ꢀC(Me)] gives S-acylated compounds (m-RS)(m-R1COS)[Fe2(CO)6]2(m4-S) (2a–h). However, if R1 in R1COCl is an electron-
withdrawing group such as EtO2C and p-O2NC6H4, the reaction produces [(m-RS)Fe2(CO)6]2(m4-S) (R=Ph (4)), [(m-
RS)Fe2(CO)6(m4-S)]2Fe2(CO)6 (R=Ph (5a), tBu (5b)) and [(m-RS)Fe2(CO)6]2(m-S-S-m) (R=tBu (6)). The same results were
achieved in the reaction by use of diacid chlorides or SO2Cl2 instead of EtO2CCOCl and p-O2NC6H4COCl. The structure of
complex (m-PhCH2S)[m-CH2ꢀC(Me)COS][Fe2(CO)6]2(m4-S) (2d) was determined by single-crystal X-ray diffraction. © 2000
Elsevier Science S.A. All rights reserved.
Keywords: Iron; Sulfur; Cluster; Synthesis; Reaction
1. Introduction
in situ at −78°C. Treatment of anions 1 with acid
chlorides R1COCl [R1=Me, Ph, PhCHꢀCH and
CH2ꢀC(Me)] formed S-acylated products (m-RS)(m-
R1COS)[Fe2(CO)6]2(m4-S) 2a–h, see Eq. (1).
We have reported synthesis of anionic complexes
[(m-RS)(m-S){Fe2(CO)6}2(m4-S)]− (1) and their reactions
with alkyl halides, Cp(CO)2FeI and acid chlorides,
yielding
the
complexes
of
type
(m-RS)(m-
R%S)[Fe2(CO)6]2(m4-S) (R%=alkyl, Cp(CO)2Fe and acyl)
[1]. In further studies on the reactivity of 1 towards acid
chlorides, we found that the reaction products were
dependent on the nature of the acid chlorides. In order
to investigate how the reaction is affected by an acid
chloride, we carried out the reaction using different acid
chlorides. The reaction of 1 with a series of diacid
chlorides was also studied. Herein we report the results.
(1)
However, when R1 is an electron-withdrawing group
such as EtO2C and p-NO2C6H4, the reaction gave a
mixture of several iron–sulfur clusters. For R=Ph,
(m-PhS)2Fe2(CO)6 (3), [(m-PhS)Fe2(CO)6]2(m4-S) (4) and
[(m-PhS)Fe2(CO)6(m4-S)]2Fe2(CO)6 (5a) were obtained.
For R=tBu, the products were [(m-tBuS)Fe2(CO)6(m4-
S)]2Fe2(CO)6 (5b), [(m-tBuS)Fe2(CO)6]2(m-S-S-m) (6) and
a minor component (7), which may be an 8Fe5S cluster
such as [(m-tBuS)Fe2(CO)6(m4-S)Fe2(CO)6]2(m4-S). Fur-
ther experiments showed that the same results could be
achieved by reaction of 1 with diacid chlorides or
2. Results and discussion
Anionic complexes [(m-RS)(m-S){Fe2(CO)6}2(m4-S)]−
(1) were prepared as described previously [1] and used
* Corresponding author. Fax: +86-0551-3631 760.
E-mail address: zxwang@ustc.edu.cn (Z.-X. Wang)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00042-5

Z.-X. Wang et al. / Journal of Organometallic Chemistry 601 (2000) 108–113
109
Scheme 1.
SO2Cl2. After this work was finished, Song and co-
workers reported the reaction of [(m-tBuS)(m-S){Fe2-
(CO)6}2(m4-S)]− with SO2Cl2, yielding [(m-tBuS)Fe2-
(CO)6(m4-S)]2Fe2(CO)6 [2]. The reaction mechanism of 1
with R1COCl (R1=EtO2C, p-NO2C6H4) might be pro-
posed as showed in Scheme 1 based on the reported
mechanism for the reaction between (m-RS)(m-
R%COS)Fe2(CO)6 and [(m-RS)(m-S)Fe2(CO)6]− [3] and
similar systems [4,5]. First, the anions 1 react with
R1COCl to form normal S-acylated products (m-RS)(m-
R1COS)[Fe2(CO)6]2(m4-S) (M1). Then M1 undergoes
nucleophilic attack on the iron atoms by the anionic
sulfur atom of excess 1 in two paths, a and b, respec-
tively. Path a gives a 6Fe4S cluster [(m-RS)Fe2(CO)6(m4-
S)]2Fe2(CO)6 and anionic fragment [(m-R1COS)-
(m-S)Fe2(CO)6]− which further decomposes. Path b
yields an 8Fe5S cluster [(m-tBuS)Fe2(CO)6(m4-
S)Fe2(CO)6]2(m4-S) and anion R1COS−. From the reac-
tion results, it seems that the path a is favored. When a
diacid chloride such as oxalyl chloride or fumaryl chlo-
ride is used in the reaction, the R1 group (ClCO or
ClCOCHꢀCH) in M1 is still strongly electron with-
drawing and makes the iron atoms more electrophilic.
However, when malonyl dichloride or succinyl chloride
is employed in the reaction, the electron-withdrawing
power of the R1 group [ClCO(CH2)n (n=1, 2)] in M1
should be close to that of Ph and Me. While the
reaction of 1 with PhCOCl or MeCOCl formed usual
products (m-RS)(m-R1COS)[Fe2(CO)6]2(m4-S) only, see
Eq. (1). Hence, we assume that the reaction with
2d was further characterized by single-crystal X-ray
diffraction (see below).
Complexes 3, 4 and 6 are known [6–8] and have been
identified by mass spectra (for 6), elemental analyses
(for 3, 4 and 6) and by comparison of their melting
1
points, H-NMR and IR spectral data with those of
authentic samples. It is worth pointing out that com-
plex 6 exists only as a diequatorial-tBu isomer accord-
1
ing to its H-NMR spectrum (unique signal at l 1.46
ppm), rather than as a mixture of two conformational
isomers due to tert-butyl groups in the axial or equato-
rial positions as indicated in the literature [8]. On the
basis of the built relationship between the structure of
1
(m-RS)2Fe2(CO)6 and H-NMR spectral data [8], 6 may
exist as either i or ii.
Complex 5a has been characterized by elemental
analysis and IR, 1H-NMR and mass spectra. Its IR
spectrum showed terminal carbonyl absorption bands
and the mass spectrum gave reasonable fragment ions
such as M+–nCO, M+–nCO–PhS and Fe6S4. Com-
plex 5b gave satisfactory microanalytical, as well as
1H-NMR and IR spectra. Its structure was also further
characterized by single-crystal X-ray diffraction, which
showed almost the same geometrical features and bond
lengths and angles as those reported in literature [2].
Complex 7 has been incompletely characterized. Its
ClCO(CH2)nCOCl (n=1, 2) proceeds through
cationic intermediate M2.
a
t
1H-NMR spectrum gave an equatorial Bu signal and
the IR spectrum showed the presence of terminal car-
bonyls. The elemental analysis supposed it to be an
8Fe5S cluster [(m-tBuS)Fe2(CO)6(m4-S)Fe2(CO)6]2(m4-S).
The mass spectrum gave only small fragment ions such
as M+–24CO–tBu and Fe6S2CMe+2 . Attempts to grow
single crystals for X-ray diffraction analysis were
unsuccessful.
Complexes 2a–h are all red solids, soluble in
methylene dichloride and petroleum ether. They have
been characterized by elemental analyses, 1H-NMR and
IR spectroscopy. The IR spectrum of each of the
compounds exhibited terminal carbonyl and thiocar-
2.1. Structure of complex 2d
1
boxylato group absorption bands. The H-NMR spec-
tra showed respective organic groups. The structure of
In order to further confirm the structures of com-
plexes 2a–h mentioned above, an X-ray diffraction

110
Z.-X. Wang et al. / Journal of Organometallic Chemistry 601 (2000) 108–113
analysis for one representative compound, 2d, was un-
dertaken. Table 1 lists the selected bond lengths and
angles. Fig. 1 shows its molecular structure. As seen
from Fig. 1, the molecule consists of two Fe2(CO)6
units joined to a spiral sulfur atom, with one of the
Fe2(CO)6 units also being bridged by a PhCH2S ligand
and the other by a CH2ꢀC(Me)COS ligand. Each
S2Fe2(CO)6 unit is butterfly shaped. The four-coordi-
nated sulfur atom is distortedly tetrahedral and hence
the two Fe2(CO)6 units are oriented approximately at
right angles to each other. The orientations of both
PhCH2 and CH2ꢀC(Me)CO groups are equatorial. The
molecular geometry and the basic geometric parameters
are very similar to those of complexes (m-tBuS)(m-
PhCH2S)[Fe2(CO)6]2(m4-S) [1], (m-PhCꢁCS)(m-EtS)[Fe2-
(CO)6]2(m4-S) [5] and (m-PhS)(m-EtS)[Fe2(CO)6]2(m4-S)
[9].
3. Experimental
All reactions were carried out under an atmosphere
of pure nitrogen using standard Schlenk techniques.
Tetrahydrofuran (THF) was distilled from sodium benz-
ophenone ketyl. Triiron dodecacarbonyl [10] and (m-
S2)Fe2(CO)6 [11] were prepared by published proce-
dures. Infrared spectra (KBr, disk) were obtained by
using a VECTOR22 spectrometer. 1H-NMR spectra
were recorded on either a Varian EM360L or a Bruker
DMX500 spectrometer with CDCl3 as solvent. Mass
spectra were taken on a HP5989A instrument. Elemen-
tal analyses were performed with a Perkin–Elmer 240C
analyzer. Melting points were uncorrected.
3.1. Synthesis of [(v-RS)(v-R1COS)[Fe2(CO)6]2(v4-S)
[2a, R=PhCH2, R1=Me; 2b, R=PhCH2, R1=Ph;
2c, R=PhCH2, R1=PhCHꢀCH; 2d, R=PhCH2,
R1=CH2ꢀC(Me); 2e, R=Ph, R1=PhCHꢀCH; 2f,
R=Ph, R1=CH2ꢀC(Me); 2g, R=tBu,
Table 1
R1=PhCHꢀCH; 2h, R=tBu, R1=CH2ꢀC(Me)]
,
Selected bond distances (A) and bond angles (°) for complex 2d
Bond distances
A
solution of triethylammonium salt of [(m-
PhCH2S)(m-CO)Fe2(CO)6]− was generated by addition
of PhCH2SH (0.21 ml, 1.79 mmol) and Et3N (0.25 ml,
1.79 mmol) to a THF (30 ml) solution of Fe3(CO)12
(0.90 g, 1.78 mmol) at room temperature (r.t.). The
solution was cooled to −78°C. To the solution was
added (m-S2)Fe2(CO)6 (0.58 g, 1.68 mmol) and stirred
for 30 min at −78°C. Subsequently CH3COCl (0.15
ml, 2.11 mmol) was added to the mixture. After stirring
overnight at r.t., the solvent was removed at reduced
pressure and the residue extracted with petroleum ether.
After removal of the solvent, the material remaining
was subjected to filtration chromatography (silica gel).
Petroleum ether eluted a minor purple band which was
not collected. Further elution with 1:9 (v/v) CH2Cl2–
petroleum ether afforded a red solid after evaporation
of the solvent, which was recrystallized from petroleum
ether to give red crystals of 2a (0.78 g, 67%), m.p.
132–134°C. Anal. Found: C, 31.96; H, 1.36.
Fe(1)–S(1)
Fe(1)–S(2)
Fe(1)–Fe(2)
Fe(2)–S(1)
Fe(2)–S(2)
2.2450(11)
2.2618(8)
2.5399(8)
2.2525(7)
2.2770(8)
Fe(3)–S(1)
Fe(3)–S(3)
Fe(3)–Fe(4)
Fe(4)–S(1)
Fe(4)–S(3)
2.2384(8)
2.2695(9)
2.5422(8)
2.2620(8)
2.2907(7)
Bond angles
S(1)–Fe(1)–S(2)
S(1)–Fe(1)–Fe(2) 55.76(2)
S(2)–Fe(1)–Fe(2) 56.26(3)
S(1)–Fe(2)–S(2)
S(1)–Fe(2)–Fe(1) 55.48(3)
S(2)–Fe(2)–Fe(1) 55.69(2)
S(1)–Fe(3)–S(3)
S(1)–Fe(3)–Fe(4) 56.05(3)
S(3)–Fe(3)–Fe(4) 56.52(2)
S(1)–Fe(4)–S(3)
76.36(3)
S(1)–Fe(4)–Fe(3)
S(3)–Fe(4)–Fe(3)
Fe(3)–S(1)–Fe(1)
Fe(3)–S(1)–Fe(2)
Fe(1)–S(1)–Fe(2)
Fe(3)–S(1)–Fe(4)
Fe(1)–S(1)–Fe(4)
Fe(2)–S(1)–Fe(4)
Fe(1)–S(2)–Fe(2)
Fe(3)–S(3)–Fe(4)
55.17(2)
55.72(3)
134.33(3)
137.53(3)
68.77(3)
68.79(3)
134.09(3)
125.48(3)
68.05(3)
67.76(3)
75.91(3)
77.98(3)
77.07(4)
1
C21H10Fe4O13S3 requires: C, 31.93; H, 1.28%. H-NMR
(60 MHz): l (ppm) 2.50 (s, 3H, CH3), 3.46 (s, 2H,
CH2), 7.10 (s, 5H, Ph). IR: w (cm−1) 2089s, 2057s,
2031vs, 1991s (Fe–CO), 1720m (CO).
Complexes 2b–h were prepared similarly. 2b, red
crystals in 62% yield, m.p. 140°C (dec.). Anal. Found:
C, 36.63; H, 1.47. C26H12Fe4O13S3 requires: C, 36.65; H,
1
1.42%. H-NMR (60 MHz): l (ppm) 3.65 (s, 2H, CH2),
7.27–8.10 (m, 10H, Ph). IR: w (cm−1) 2085s, 2061s,
2036vs, 2000s, 1989s, 1981s (Fe–CO), 1677m (CO). 2c,
deep red crystals in 46% yield, m.p. 157–158°C. Anal.
Found: C, 38.73; H, 1.77. C28H14Fe4O13S3 requires: C,
1
38.30; H, 1.61%. H-NMR (500 MHz): l (ppm) 3.63,
3.72 (s, s, 2H, CH2), 6.75 (s, 1H, CH), 7.26–7.54 (m,
Fig. 1. ORTEP view of 2d, drawn with 30% probability ellipsoids.
10H, Ph), 7.84 (s, 1H, CH). IR: w (cm−1) 2084s, 2052s,

Z.-X. Wang et al. / Journal of Organometallic Chemistry 601 (2000) 108–113
111
1
2036vs, 1998s, 1985s (Fe–CO), 1666m (CO). 2d, red
crystals in 51% yield, m.p. 165–167°C. Anal. Found: C,
33.70; H, 1.52. C23H12Fe4O13S3 requires: C, 33.86; H,
1.48%. 1H-NMR (500 MHz): l (ppm) 1.95 (s, 3H,
CH3),3.63, 3.74 (s, s, 2H, CH2), 6.04, 6.53 (s, s, 2H,
ꢀCH2), 7.38 (s, 5H, Ph). IR: w (cm−1) 2087s, 2054s,
2029vs, 1990s (Fe–CO), 1681m (CO). 2e, deep red
crystals in 48% yield, m.p. 130–131°C. Anal. Found: C,
37.76; H, 1.47. C27H12Fe4O13S3 requires: C, 37.53; H,
C18H10Fe2O6S2 requires: C, 43.41; H, 2.02%. H-NMR
(60 MHz): l (ppm) 7.13 (s, 10H, Ph). IR: w (cm−1
)
2074s, 2036vs, 2008s, 1982vs, 1971s. 4: m.p.
150°C(dec.). Anal. Found: C, 35.30; H, 1.36.
1
C24H10Fe4O12S3 requires: C, 35.59; H, 1.24%. H-NMR
(60 MHz): l (ppm) 7.20 (s, 10H, Ph).IR: w (cm−1
)
2085s, 2058s, 2039vs, 1996s, 1978s. 5a: m.p. 150°C
(dec.). Anal. Found: C, 31.94; H, 1.05. C30H10Fe6O18S4
requires: C, 32.12; H, 0.90%. H-NMR (60 MHz): l
1
1
1.40%. H-NMR (500 MHz): l (ppm) 6.72 (d, J=11.5
(ppm) 7.12 (s, 10H, Ph). IR: w (cm−1) 2088w, 2073s,
2060s, 2044vs, 1999vs, 1977s. MS (EI), m/z (relative
intensity): 956 (M+–2CO–PhS−1, 0.11), 928 (M+–
3CO–PhS−1, 0.13), 872 (M+–5CO–PhS−1, 0.20),
787 (M+–12CO+1, 0.54), 759 (M+–13CO+1, 0.15),
731 (M+–14CO+1, 0.33), 703 (M+–15CO+1, 0.19),
675 (M+–16CO+1, 0.17), 647 (M+–17CO+1, 0.12),
619 (M+–18CO+1, 0.62), 561 (M+–9CO–Ph–Fe3S2,
0.16), 464 (Fe6S+4 , 1.11), 329 (Fe2(CO)5Ph+, 1.19), 242
(FeSPh+2 , 0.58), 186 (SPh2+, 100), 154 (Ph+2 , 36.10), 77
(Ph+, 18.67), 65 (C5H+5 , 9.84), 56 (Fe+, 5.90), 51
(C4H+3 , 20.78).
Hz, 1H, CH), 7.19, 7.30 (s, s, 5H, Ph), 7.39, 7.51 (s, s,
5H, Ph), 7.85 (d, J=12.0 Hz, 1H, CH). IR: w (cm−1
)
2086s, 2060s, 2036vs, 2001s, 1979s (Fe–CO), 1665m
(CO). 2f, red crystals in 54% yield, m.p. 90–92°C. Anal.
Found: C, 32.57; H, 1.35. C22H10Fe4O13S3 requires: C,
1
32.95; H, 1.26%. H-NMR (500 MHz): l (ppm) 1.96 (s,
3H, CH3), 6.07, 6.59 (s, s, 2H, ꢀCH2), 7.25, 7.35 (s, s,
5H, Ph). IR: w (cm−1) 2086s, 2063s, 2039vs, 1996s
(Fe–CO), 1677m (CO). 2g, red crystals in 47% yield,
m.p. 155–157°C. Anal. Found: C, 35.92; H, 1.94.
1
C25H16Fe4O13S3 requires: C, 35.58; H, 1.91%. H-NMR
t
(500 MHz): l (ppm) 1.44 (s, 9H, Bu), 6.70 (d, J=15.0
The reaction of [(m-PhS)(m-S){Fe2(CO)6}2(m4-S)]−
with EtO2CCOCl followed the same procedure as de-
scribed above. After work-up, complexes 3 (39%), 4
(10%) and 5a (6%) were obtained.
Hz, 1H, CH), 7.39, 7.50 (s, s, 5H, Ph), 7.83 (d, J=14.6
Hz, 1H, CH). IR: w (cm−1) 2084s, 2053s, 2037vs, 2002s,
1988s, 1980s (Fe–CO), 1660m (CO). 2h, deep red crys-
tals in 81% yield, m.p. 168–170°C. Anal. Found: C,
30.52; H, 1.78. C20H14Fe4O13S3 requires: C, 30.72; H,
3.3. Reaction of [(v-PhS)(v-S){Fe2(CO)6}2(v4-S)]−
1
t
1.80%. H-NMR (500 MHz): l (ppm) 1.48 (s, 9H, Bu),
1.94 (s, 3H, Me), 6.03, 6.55 (s, s, 2H, ꢀCH2). IR: w
(cm−1) 2084s, 2053s, 2032vs, 2013s, 1990s, 1980s (Fe–
CO), 1681m (CO).
with organic diacid chlorides
(i) [(m-PhS)(m-S){Fe2(CO)6}2(m4-S)]− was prepared
according to the same procedure as described above
from (m-S2)Fe2(CO)6 (0.48 g, 1.40 mmol) and [(m-
PhS)(m-CO)Fe2(CO)6]− derived from Fe3(CO)12 (0.73 g,
1.45 mmol), PhSH (0.15 ml, 1.46 mmol) and Et3N (0.20
ml, 1.43 mmol) in THF (30 ml). To the solution was
added oxalyl chloride (0.06 ml, 0.68 mmol) at −78°C
and stirred overnight at r.t. After the same work-up as
described above, complexes 3 (0.16 g, 47%), 4 (0.08 g,
15%) and 5a (0.07 g, 9%) were obtained.
3.2. Reaction of [(v-PhS)(v-S){Fe2(CO)6}2(v4-S)]−
with p-NO2C6H4COCl and EtO2CCOCl
[(m-PhS)(m-S){Fe2(CO)6}2(m4-S)]− was prepared ac-
cording to the same procedure as described above from
(m-S2)Fe2(CO)6 (0.48 g, 1.40 mmol) and [(m-PhS)(m-
CO)Fe2(CO)6]− derived from Fe3(CO)12 (0.74 g, 1.45
mmol), PhSH (0.15 ml, 1.46 mmol) and Et3N (0.20 ml,
1.43 mmol) in THF (30 ml). To the solution was added
p-NO2C6H4COCl (0.27 g, 1.45 mmol) at −78°C. The
mixture was warmed to r.t. and stirred overnight. The
solvent was removed at reduced pressure and the
residue extracted with petroleum ether. After removal
of the solvent, the material remaining was subjected to
filtration chromatography (silica gel). Petroleum ether
eluted a minor purple band which was not collected.
Further elution with petroleum ether and 1:9 (v/v)
CH2Cl2–petroleum ether developed three red bands
successively. The first band gave red crystalline (m-
PhS)2Fe2(CO)6 (3) (0.11 g, 32%). The second band gave
[(m-PhS)Fe2(CO)6]2(m4-S) (4) (0.08 g, 14%) as red crys-
tals. The third band gave red–brown crystals of [(m-
PhS)Fe2(CO)6(m4-S)]2Fe2(CO)6 (5a) (0.06 g, 8%). 3: m.p.
130–132°C. Anal. Found: C, 43.40; H, 2.14.
(ii) The reaction of [(m-PhS)(m-S){Fe2(CO)6}2(m4-S)]−
with fumaryl chloride followed the same procedure as
described above, but fumaryl chloride was used instead
of oxalyl chloride. After work-up, complexes 3 (69%), 4
(12%) and 5a (2%) were obtained.
(iii) The reaction of [(m-PhS)(m-S){Fe2(CO)6}2(m4-S)]−
with malonyl dichloride followed the same procedure as
described in (i), but malonyl dichloride was used in-
stead of oxalyl chloride. After the same work-up as
described above, complexes 3 (62%), 4 (16%) and 5a
(3%) were obtained.
(iv) The reaction of [(m-PhS)(m-S){Fe2(CO)6}2(m4-S)]−
with succinyl chloride was carried out according to the
same procedure as described in (i), but succinyl chloride
was used instead of oxalyl chloride. After the same
work-up, complexes 3 (43%), 4 (12%) and 5a (3%) were
obtained.

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Z.-X. Wang et al. / Journal of Organometallic Chemistry 601 (2000) 108–113
3.4. Reaction of [(v-tBuS)(v-S){Fe2(CO)6}2(v4-S)]−
with EtO2CCOCl
tBuS)(m-CO)Fe2(CO)6]− derived from Fe3(CO)12 (0.87
t
g, 1.73 mmol), BuSH (0.20 ml, 1.77 mmol) and Et3N
(0.25 ml, 1.79 mmol) in THF (30 ml). To the solution
was added oxalyl chloride (0.08 ml, 0.9 mmol) at
−78°C and stirred overnight at r.t. After the same
work-up as described above, complexes 6 (0.06 g, 9%),
5b (0.33 g, 36%) and 7 (0.06 g, 5%) were obtained.
(ii) The reaction of [(m-tBuS)(m-S){Fe2(CO)6}2(m4-S)]−
with fumaryl chloride followed the same procedure as
described above. After work-up, complexes 6 (26%), 5b
(25%) and 7 (6%) were obtained.
A solution of triethylammonium salt of [(m-tBuS)(m-
t
CO)Fe2(CO)6]− was generated by addition of BuSH
(0.16 ml, 1.42 mmol) and Et3N (0.20 ml, 1.43 mmol) to
a THF (30 ml) solution of Fe3(CO)12 (0.72 g, 1.43
mmol) at r.t. The solution was cooled to −78°C. To
the solution was added (m-S2)Fe2(CO)6 (0.48 g, 1.40
mmol) and stirred for 30 min at −78°C. Subsequently
EtO2CCOCl (0.16 ml, 1.43 mmol) was added to the
mixture. After stirring overnight at r.t., the solvent was
removed at reduced pressure and the residue extracted
with petroleum ether. After removal of the solvent, the
material remaining was subjected to filtration chro-
matography (silica gel). Petroleum ether eluted a minor
purple band which was not collected. Further elution
with petroleum ether and then 1:9 (v/v) CH2Cl2–
petroleum ether moved three red bands successively.
The first band gave [(m-tBuS)Fe2(CO)6]2(m-S-S-m) (6)
(0.05 g, 9%) as purplish–red crystals. The second band
gave red–purple crystals [(m-tBuS)Fe2(CO)6(m4-S)]2-
Fe2(CO)6 (5b) (0.12 g, 16%) and the third band af-
forded 7 (0.07 g, 7%) as a red powder. 6: m.p. 137–
138°C. Anal. Found: C, 29.58; H, 2.27. C20H18Fe4O12S4
(iii) The THF solution of [(m-tBuS)(m-S){Fe2-
(CO)6}2(m4-S)]− was treated with malonyl dichloride
according to the procedure described above to give,
after work-up, 5b (19%), 6 (12%) and 7 (10%).
(iv) The reaction of [(m-tBuS)(m-S){Fe2(CO)6}2(m4-
S)]− with succinyl chloride was carried out similarly.
After the same work-up, complexes 5b (32%), 6 (18%)
and 7 (8%) were obtained.
3.6. Crystal structure determination of complex 2d
Suitable crystals of complex 2d were grown from
petroleum ether–CH2Cl2 solution at r.t. Data were
collected on a Siemens P4 four-circle diffractometer
using monochromated Mo–Ka radiation. A semi-em-
pirical absorption correction was applied to the data. A
summary of data collection details and crystal data is
given in Table 2. The structure was solved by direct
1
requires: C, 29.95; H, 2.26%. H-NMR (60 MHz): l
t
(ppm) 1.47 (s, 18H, Bu). IR: w (cm−1) 2081m, 2056s,
2037vs, 2016s, 1990vs, 1974s. MS (EI), m/z (relative
intensity): 634 (M+–6CO, 0.12), 606 (M+–7CO, 0.14),
578 (M+–8CO, 0.24), 550 (M+–9CO, 0.19), 522 (M+–
10CO, 0.27), 494 (M+–11CO, 0.85), 466 (M+–12CO,
0.35), 409 (M+–12CO–tBu, 0.23), 352 (M+–12CO–
2tBu, 1.64), 320 (M+–12CO–2tBu–S, 0.82), 207 (M+–
Table 2
Crystal data and refinement for complex 2d
Formula
C23H13Fe4O13S3
816.91
Triclinic
12CO–2tBu–SFe2,
0.58),
176
Formula weight
Crystal system
Space group
(M+–12CO–2tBu–S2Fe2, 0.68), 90 (tBuSH+, 6.93), 75
(tBuSH+–Me, 3.89), 56 (Fe+, 44.99), 41 (C3H+5 , 100).
5b: m.p. 170°C (dec.). Anal. Found: C, 28.64; H, 1.69.
(
P1
Unit cell dimensions
1
,
a (A)
9.181(2)
11.455(2)
15.795(3)
74.03(3)
74.53(3)
84.77(3)
4072.5(9)
2
C26H18Fe6O18S4 requires: C, 28.87; H, 1.68%. H-NMR
,
b (A)
(60 MHz): l (ppm) 1.48 (s, 18H, Bu). IR: w (cm−1
)
t
,
c (A)
h (°)
i (°)
k (°)
V (A )
2087w, 2066vs, 2041vs, 1989vs, 1975s. 7: m.p. 190°C
(dec.). Anal. Found: C, 27.28; H, 1.50. C32H18Fe8O24S5
1
requires: C, 27.58; H, 1.30%. H-NMR (60 MHz): l
3
t
(ppm) 1.42 (s, 18H, Bu). IR: w (cm−1) 2091w, 2080m,
,
Z
2057vs, 2039vs, 2022s, 1988vs. MS (EI), m/z (relative
intensity): 665 (M+–24CO–tBu, 0.97), 442 (M+–
20CO–tBu–Fe4S3, 0.71), 315 (Fe2S2(CO)4CMe+, 0.65),
244 (Fe2S2(CO)2C+, 2.29), 147 (tBu2S++1, 2.97), 84
(Fe(CO)+, 26.38), 71 (C5H1+1, 28.66), 57 (tBu +, 89.76),
41 (C3H+5 , 100).
Crystal size (mm)
0.26×0.22×0.20
0.71073
2.112
294(2)
4832
,
Radiation u (A)
v(Mo–Ka) (mm−1
Temperature (K)
Total reflections
)
Independent reflections
4827
Reflections with I\2|(I)
4441
Scan type
2qmax (°)
aR1
ꢀ scan
50.11
0.0518
0.1546
3.5. Reaction of [(v-tBuS)(v-S){Fe2(CO)6}2(v4-S)]−
with organic diacid chlorides
bwR2
−3
,
Largest differences peak and hole (e A
)
0.422 and −0.469
(i) [(m-tBuS)(m-S){Fe2(CO)6}2(m4-S)]− was prepared
according to the same procedure as described above
from (m-S2)Fe2(CO)6 (0.59 g, 1.71 mmol) and [(m-
a R1=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ.
b wR2=[ꢀw(Fo2−Fc2)2/ꢀwFo4]1/2
.

Z.-X. Wang et al. / Journal of Organometallic Chemistry 601 (2000) 108–113
113
methods and was refined by full-matrix least-squares
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4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 136814. Copies of this infor-
mation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (fax: +44-1223-336 033; email: de-
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Acknowledgements
We thank the Educational Ministry of China and the
Chinese Academy of Sciences for financial support.
.