Syntheses of novel Fe/S clusters via reactions of Fe3(CO) 12 and [Et4N][Ph2PCS2] with electrophiles

Article abstract of DOI:10.1016/j.jorganchem.2012.05.030

Reaction of Fe₃(CO)₁₂ with [NEt₄][Ph ₂PCS₂] in THF at room temperature forms a red-brown solution. Reactions of the solution with a series of electrophiles E-X (E-X = MeI, PhCH₂Br, CH₃COCl, PhCOCl) generate the corresponding clusters Fe₂(CO)₆(μ-k²P,C:k ²S-Ph₂PCSSE) (1, E = CH₃; 2, E = CH ₂Ph; 3, E = COCH₃; 4, E = COPh). The reaction of 4 with PPh₃ in the presence of Me₃NO affords the cluster [Fe ₂(CO)₅(μ-k²P,C:k²S-Ph ₂PCSSCOPh)(k-PPh₃)] (5) in which PPh₃ is coordinated to the iron center with the PPh₂ group. The tandem reaction of the solution with CS₂ and with MeI gives the cluster Fe₂(CO)₅(μ-k²P,C:k²S-kS-Ph ₂PCSSC(S)SMe) (6). The tandem reaction of the solution with Fe ₃(CO)₁₂ and with PPh₂Cl forms the cluster Fe₂(CO)₆(μ-k²P,C:k²S-Ph ₂PCSS-k²S-)Fe₂(CO)₆(μ-PPh ₂) (7). The reaction of the solution with PhCClN(4-C ₆H₄Cl) gives clusters Fe₂(CO) ₆(μ-k²P,C:k²S-Ph₂PCHS) (8), Fe₂(CO)₅(μ-k²P,C:k²S-kN-Ph ₂PCSSCPhN(4-C₆H₄Cl)) (9) and Fe ₂(CO)₅(μ-k²P,C:k²S-kS-Ph ₂PCSN(4-C₆H₄Cl)CPhS) (10). Because the structures of all novel complexes have been unequivocally determined by X-ray crystallography, reactions of Fe₃(CO)₁₂ and [Et ₄N][Ph₂PCS₂] with electrophiles have provided new methods for synthesizing novel Fe/S clusters.

Full text of DOI:10.1016/j.jorganchem.2012.05.030

Journal of Organometallic Chemistry 716 (2012) 39e48
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Syntheses of novel Fe/S clusters via reactions of Fe3(CO)12 and [Et4N][Ph2PCS2]
with electrophiles
*
Yao-Cheng Shi , Huan-Ren Cheng, Hao Tan
College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of Fe3(CO)12 with [NEt4][Ph2PCS2] in THF at room temperature forms a red-brown solution.
Received 9 January 2012
Received in revised form
21 May 2012
Reactions of the solution with a series of electrophiles E-X (E-X ¼ MeI, PhCH2Br, CH3COCl, PhCOCl)
generate the corresponding clusters Fe2(CO)6(
m
-k2P,C:k2S-Ph2PCSSE) (1, E ¼ CH3; 2, E ¼ CH2Ph; 3,
E ¼ COCH3; 4, E ¼ COPh). The reaction of 4 with PPh3 in the presence of Me3NO affords the cluster
Accepted 24 May 2012
[Fe2(CO)5(
the PPh2 group. The tandem reaction of the solution with CS2 and with MeI gives the cluster
Fe2(CO)5(
-k2P,C:k2S-kS-Ph2PCSSC(]S)SMe) (6). The tandem reaction of the solution with Fe3(CO)12 and
with PPh2Cl forms the cluster Fe2(CO)6( -PPh2) (7). The reaction
-k2P,C:k2S-Ph2PCSS-k2S-)Fe2(CO)6(
of the solution with PhCCl]N(4-C6H4Cl) gives clusters Fe2(CO)6(
-k2P,C:k2S-Ph2PCHS) (8),
Fe2(CO)5(
-k2P,C:k2S-kN-Ph2PCSSCPh]N(4-C6H4Cl)) (9) and Fe2(CO)5( -k2P,C:k2S-kS-Ph2PCSN(4-C6H4Cl)
m
-k2P,C:k2S-Ph2PCSSCOPh)(k-PPh3)] (5) in which PPh3 is coordinated to the iron center with
Keywords:
Cluster
Ironeiron bond
Carbonyl ligand
Organometallic compound
Hydrogenase
m
m
m
m
m
m
CPh]S) (10). Because the structures of all novel complexes have been unequivocally determined by X-
ray crystallography, reactions of Fe3(CO)12 and [Et4N][Ph2PCS2] with electrophiles have provided new
methods for synthesizing novel Fe/S clusters.
Synthetic methodology
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
E will achieve a fine-tuning of the structural and electronic featur-
es of the coordination sphere of synthetic diiron molecules.
Recently, Fe/S cluster complexes have attracted considerable
attention, because of their interesting chemistry and particularly
their close relevance to the modeling study of the active site of
[FeeFe] hydrogenases [1e6]. Moreover, until now, few efficient
electrocatalysts have been obtained and the mechanism of the
natural production/uptake of hydrogen remains unclear [2]. There-
fore, novel structural and chemical models are still necessary to gain
a better understanding of the protonation mechanisms implied at
the molecular level. Since a general method for synthesizing a diiron
Heteroallyl anions of the general type GeC(]Y)eZꢀ (G ¼ potential
donor group; Y ¼ S, Se; Z ¼ S, Se, NR, CHR) are potential six-electron
donors, which may act as anion Lꢀ. Moreover, they can be easily
prepared from inexpensive and readily available starting materials.
As a result, through a judicious choice of nucleophile Gꢀ and het-
eroallene Y]C]Z used in their synthesis, the steric and electronic
properties of ligands of this type can be tuned and further func-
tionalization readily introduced by a modification of electrophile
E-X. In view of no reports on heteroallyl anions of the general type
GeC(]Y)eZꢀ with iron carbonyls [16e19], we have initiated the
project on reactions of heteroallyl anions GeC(]Y)eZꢀ with iron
carbonyls in order to confirm the above idea and to develop the
synthetic methodology of Fe-cluster complexes. As part of the
project, herein we report reactions of Fe3(CO)12 and [Ph2PCS2]ꢀ with
electrophiles [20,21].
hexacarbonyl complex [(
of the general type [(
m
m
-E)(
-CO)(
m
-Nu)Fe2(CO)6] from reaction of anion
m
-Nu)Fe2(CO)6]ꢀ generated from
Fe3(CO)12 and a three-electron donor Nuꢀ (such as RSꢀ, RSeꢀ and
RTeꢀ) with a three-electron electrophile E-X (typically, RSCl, RCOCl,
Ph2PCl and PhCCl]NPh) has been developed by Seyferth and Song
[7e15], it may be speculated that a six-electron bridging donor
L0 could give a diiron hexacarbonyl complex [(
Furthermore, reaction of a six-electron bridging anion Lꢀ with the
iron carbonyl may result in the formation of a cluster anion [( -L)
Fe2(CO)6]ꢀ. The resulting cluster anion reacts with an electrophile
E-X to give a novel complex [( -LE)Fe2(CO)6]. Changes of L and
m
-L0)Fe2(CO)6].
2. Experimental section
m
2.1. General procedures
m
All reactions were carried out under a prepurified N2 atmo-
sphere with standard Schlenk techniques. All solvents employed
were dried by refluxing over appropriate drying agents and stored
* Corresponding author. Tel./fax: þ86 0514 87857939.
E-mail address: ycshi@yzu.edu.cn (Y.-C. Shi).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.05.030

40
Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
under an N2 atmosphere. THF was distilled from sodium-
benzophenone, petroleum ether (60e90 ꢁC) and CH2Cl2 from
P2O5. Fe3(CO)12 [22], [NEt4][PPh2CS2] [18] and PhCCl]N(4-C6H4Cl)
were prepared according to literature procedures [23e25]. The
progress of all reactions was monitored by TLC (silica gel H,
2.5. Synthesis of complex 4
The same procedure was used, but PhCOCl was the added
electrophile. The product 4, an orange solid (0.924 g), mp
150e152 ꢁC, was obtained in 48% yield. Anal. Calcd for C26H15Fe2
-
300e400 mesh). 1H NMR (500 MHz), 31P NMR (202.5 MHz) and 13
C
PO7S2: C, 48.33; H, 2.34; found: C, 48.26; H, 2.41. IR (KBr disk):
{H} NMR (125.8 MHz) spectra were carried out on a Bruker Avance
500 spectrometer using TMS or 85% H3PO4 as an external standard
in CDCl3. IR spectra were recorded on a Bruker Tensor 27 spec-
trometer as KBr disks in the range 400e4000 cmꢀ1. HR-MS data
were recorded on a Bruker Maxis spectrometer. Analyses for C, H
and N were performed on a PE 2400 Series III instrument. Melting
n
(C^O) 2066 (vs), 1986 (vs), 1954 (vs),
NMR (500 MHz, CDCl3, TMS): 7.32e7.36 (m, 5H, C6H5), 7.47e7.53
(m, 5H, C6H5), 7.58e7.69 (m, 5H, C6H5) ppm. 31P NMR (202.5 MHz,
CDCl3, 85% H3PO4):
37.55 (s) ppm. 13C NMR (125.8 MHz, CDCl3,
TMS):
n
(C]O) 1678 (m) cmꢀ1. 1H
d
d
d
127.1 (s), 128.1 (d, J ¼ 9.9 Hz), 128.6 (d, J ¼ 9.1 Hz), 128.7 (s),
131.1 (s), 131.7 (s), 132.2 (d, J ¼ 9.3 Hz), 133.0 (d, J ¼ 10.2 Hz), 133.5
(s), 135.7 (s) (3C6H5), 134.9 (d, 1JCeP ¼ 26.7 Hz, PCS2), 188.7 (C]O),
210.5 (6C^O) ppm.
points were measured on
uncorrected.
a Yanagimoto apparatus and are
2.6. Synthesis of complex 5
2.2. Synthesis of complex 1
Thesolutionof0.194g(0.3mmol)4 and0.079g(0.3mmol)Ph3Pin
25mLofTHF inthe presenceof 0.023 g(0.3 mmol) Me3NOwasstirred
for 2 h at room temperature. After the solvent was removed in vacuo,
the resulting residue was subjected to chromatography (silica gel) to
afford an orange solid of 5 (0.248 g), mp, 148e150 ꢁC, in 94% yield.
Anal. Calcd for C43H30Fe2P2O6S2: C, 58.66; H, 3.43; found: C, 58.28; H,
A 50-mL Schlenk flask equipped with a stir bar and serum cap-
was charged with 1.50 (2.98 mmol) of Fe3(CO)12
g
,
1.17 g (2.98 mmol) of [NEt4][PPh2CS2] and 25 mL of THF. The mixture
was stirred for 1 h at room temperature to form a red-brown
solution. To this solution was added two equivalents of an electro-
phile (iodomethane). The solution was stirred for 20 h and then
filtered. After the solvent was removed under reduced pressure, the
resulting residue was chromatographed by TLC on silica gel. Elution
with petroleum ether gave one major band which was recrystal-
lized from deoxygenated petroleum ether (60e90 ꢁC) and CH2Cl2 to
afford an orange solid of 1 (0.762 g), mp, 180e182 ꢁC, in 46% yield.
Anal. Calcd for C20H13Fe2PO6S2: C, 43.20; H, 2.36; found: C, 43.35; H,
3.52. IR (KBr disk):
n
(C^O) 2034 (vs), 1980 (vs), 1922 (vs),
n(C]O)
1685 (m) cmꢀ1 1H NMR (500 MHz, D3COCD3, TMS):
.
d
7.13e7.17,
7.24e7.36, 7.41e7.46, 7.47e7.61, 7.65e7.69 (5m, 30H, 6C6H5) ppm.
31PNMR(202.5MHz,D3COCD3, 85%H3PO4):
d
40.13(d, 2JPeP ¼ 51.0Hz,
2
PPh2), 59.88 (d, JPeP ¼ 51.0 Hz, PPh3) ppm. 13C NMR (125.8 MHz,
D3COCD3, TMS):
d
128.6 (s),129.6 (d, J ¼ 12.6 Hz),130.3 (d, J ¼ 12.6 Hz),
2.47. IR (KBr disk):
NMR (500 MHz, CDCl3, TMS):
2C6H5) ppm. 31P NMR (202.5 MHz, CDCl3, 85% H3PO4):
ppm. 13C NMR (125.8 MHz, CDCl3, TMS):
21.6 (CH3), 128.7 (d,
n
(C^O) 2062 (vs), 2000 (vs), 1973 (vs) cmꢀ1. 1H
1.69 (s, 3H, CH3), 7.36e7.92 (5m,10H,
37.01 (s)
130.7 (s), 132.0 (s), 132.3 (s), 133.2 (s), 134.5 (d, J ¼ 12.6 Hz), 134.6 (d,
J ¼ 12.6 Hz), 135.2 (d, J ¼ 12.6 Hz), 135.4 (s) (6C6H5), 136.4 (d,
1JCeP ¼ 50.0 Hz, PCS2), 189.6 (C]O), 207.0 (5C^O) ppm.
d
d
d
2.7. Synthesis of complex 6
J ¼ 2.4 Hz), 128.8 (d, J ¼ 4.0 Hz), 131.4 (d, J ¼ 2.5 Hz), 131.6 (s), 131.9
(d, J ¼ 1.9 Hz), 132.0 (s), 132.4 (d, J ¼ 9.6 Hz), 132.5 (d, J ¼ 8.9 Hz)
(2C6H5), 136.7 (d, 1JCeP ¼ 23.3 Hz, PCS2), 210.4 (6C^O) ppm.
The Fe3(CO)12/[NEt4][PPh2CS2] solution was prepared as above;
to this solution was added 0.454 g (5.96 mmol) of carbon disulfide.
The mixture was stirred for 1 h and then 0.846 g (5.96 mmol) of
iodomethane was added. Stirring was continued for 20 h and then
the solution was filtered. After the solvent was removed under
reduced pressure, the resulting residue was chromatographed by
TLC on silica gel. Petroleum ether (60e90 ꢁC) eluted a purple band
which gave 6 (0.702 g), mp 194e197 ꢁC, in 39% yield. Anal. Calcd for
C20H13Fe2PO5S4: C, 39.76; H, 2.17; found: C, 39.52; H, 2.34. IR (KBr
2.3. Synthesis of complex 2
The same procedure was used, but PhCH2Br was the added
electrophile. The product 2, an orange solid (0.886 g), mp
174e176 ꢁC, was obtained in 47% yield. Anal. Calcd for
C26H17Fe2O6PS2: C, 49.40; H, 2.71; found: C, 49.32; H, 2.53. IR (KBr
(C^O) 2044 (vs), 1979 (vs), 1921 (vs) cmꢀ1
2.84 (s, 3H, CH3), 7.45e7.59 (m, 10H,
36.29 (s)
.
1H NMR
disk):
n
(C^O) 2064 (vs), 2045 (s), 2022 (s), 1982 (s) cmꢀ1. 1H NMR
disk):
(500 MHz, CDCl3, TMS):
2C6H5) ppm. 31P NMR (202.5 MHz, CDCl3, 85% H3PO4):
ppm. 13C NMR (125.8 MHz, CDCl3, TMS):
21.76 (CH3), 128.7 (d,
n
2
(500 MHz, CDCl3, TMS): 3.09, 3.45 (dd, JHeH ¼ 11.9 Hz, 2H, CH2),
6.94e7.99 (4m, 15H, 3C6H5) ppm. 31P NMR (202.5 MHz, CDCl3, 85%
H3PO4): 37.26 (s) ppm. 13C NMR (125.8 MHz, CDCl3, TMS): 43.33
(CH2), 127.2 (s), 128.4 (s), 128.9 (d, J ¼ 9.9 Hz), 131.6 (s), 131.9 (s),
d
d
d
J ¼ 9.8 Hz), 129.0 (d, J ¼ 8.8 Hz), 130.7 (d, J ¼ 8.8 Hz), 131.0 (s), 131.7
1
132.6 (d, J ¼ 8.1 Hz), 136.3 (s) (3C6H5), 136.8 (d, JCeP ¼ 23.1 Hz,
1
(s), 132.3 (d, J ¼ 9.1 Hz) (2C6H5), 138.0 (d, JCeP ¼ 26.4 Hz, PCS2),
PCS2), 210.3 (6C^O) ppm.
210.7, 214.0, 217.3, 217.4, 223.8 (C]S, 5C^O) ppm.
2.8. Synthesis of complex 7
2.4. Synthesis of complex 3
The same procedure was used with CH3COCl as the added
electrophile. The orange solid product 3 (0.766 g), mp 160e162 ꢁC,
was obtained in 44% yield. Anal. Calcd for C21H13Fe2O7PS2: C, 43.18;
The Fe3(CO)12/[NEt4][PPh2CS2] solution was prepared as above;
to this solution was added 1.50 g (2.98 mmol) of Fe3(CO)12. The
mixture was stirred for 1 h and then 1.315 g (5.96 mmol) of Ph2PCl
was added. Stirring was continued for 20 h and then the solution
was filtered. After removal of the solvent under vacuum, the
resulting residue was subjected to chromatography (silica gel).
Petroleum ether (60e90 ꢁC) eluted a brown band which afforded 7
(1.049 g), mp 220 (dec.) ꢁC, in 35% yield. Anal. Calcd for
C37H20Fe4P2O12S2: C, 44.18; H, 2.00; found: C, 44.02; H, 1.86. IR (KBr
H, 2.24; found: C, 43.34; H, 2.45. IR (KBr disk):
n(C^O) 2064 (vs),
2019 (s), 1994 (s), 1969 (s), 1949 (s),
n
(C]O) 1711 (m) cmꢀ1. 1H NMR
(500 MHz, CDCl3, TMS): 1.99 (s, 3H, CH3), 7.25e7.59 (m, 10H,
2C6H5) ppm. 31P NMR (202.5 MHz, CDCl3, 85% H3PO4): 36.91
(s) ppm. 13C NMR (125.8 MHz, CDCl3, TMS): 29.0 (CH3), 128.0
(d, J ¼ 9.3 Hz), 128.4 (d, J ¼ 10.2 Hz), 131.2 (s), 131.7 (s), 132.2
(d, J ¼ 8.7 Hz), 133.1 (d, J ¼ 9.7 Hz) (2C6H5), 134.9 (d, 1JCeP ¼ 26.5 Hz,
PCS2), 192.3 (C]O), 210.4 (6C^O) ppm.
disk):
n
(C^O) 2061 (vs), 2022 (vs), 1996 (vs), 1966 (vs) cmꢀ1
.
1H
NMR (500 MHz, D3COCD3, TMS):
d
7.15e7.89 (5m, 20H, 4C6H5) ppm.

Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
41
31P NMR (202.5 MHz, D3COCD3, 85% H3PO4):
142.45 (s,
-Ph2P) ppm. 13C NMR (125.8 MHz, CDCl3, TMS):
(s), 128.8 (s), 129.6 (s), 129.8 (s), 129.9 (s), 130.5 (s), 130.8 (s), 130.9
(s), 131.6 (s), 131.7 (s), 131.8 (s), 132.2 (s), 133.1 (s) (4C6H5), 134.4 (d,
1JCeP ¼ 30.4 Hz, PCS2), 206.0, 213.7 (12C^O) ppm.
d
42.07 (s, Ph2P),
128.7
n
(C^O) 2035 (vs), 1979 (s), 1920 (s) cmꢀ1. 1H NMR (500 MHz, CDCl3,
m
d
TMS): 7.05e7.21, 7.34e7.50 (2m, 19H, C6H4Cl, 3C6H5) ppm. 31P NMR
(202.5 MHz, CDCl3, 85% H3PO4): 46.55 (s) ppm. 13C NMR
(125.8 MHz, CDCl3, TMS): 127.4 (s), 127.8 (s), 127.9 (s), 128.2
(d, JCeP ¼ 9 Hz), 128.5 (d, JCeP ¼ 10 Hz), 130.1 (s), 130.3 (s), 131.1 (s),
132.0 (d, JCeP ¼ 9.2 Hz), 132.3 (d, JCeP ¼ 9.6 Hz), 133.9 (s), 136.2 (s),
139.2 (s), 151.0 (s) (C6H4Cl, 3C6H5), 134.2 (d, 1JCeP ¼ 17.4 Hz, PCS),
2.9. Syntheses of complexes 8e10
2
202.5 (s, C]S), 211.5, 215.2 (s, s, Fe(CO)2), 217.6 (d, JCeP ¼ 14 Hz,
Fe(CO)3) ppm.
The Fe3(CO)12/[NEt4][PPh2CS2] solution was prepared as
above; to this solution was added 1.491 g (5.96 mmol) of
PhC(Cl)]N(4-C6H4Cl). Stirring was continued for 20 h and then the
solution was filtered. After the solvent was removed under reduced
pressure, the resulting residue was subjected to chromatography
(silica gel). Elution with petroleum ether (60e90 ꢁC) gave an orange
solid of 8 (0.167 g, in 11% yield, mp, 118e120 ꢁC), further elution
with petroleum ether (60e90 ꢁC) and CH2Cl2 (1:3, v/v) afforded
a brown solid of 9 (0.824 g, in 38% yield, mp, 194e196 ꢁC), and
a purple solid of 10 (0.282 g, in 13% yield, mp, 236e238 ꢁC) in the
decreased order of Rf values. Anal. Calcd for C19H11Fe2O6PS (8): C,
2.10. X-ray structure determinations of 1e10
Single crystals of 1e10 suitable for X-ray diffraction analyses
were grown by slow evaporation of the CH2Cl2-petroleum ether
solutions of 1e10 at 0e4 ꢁC. For each of complexes, a selected single
crystal was mounted on a Bruker APEX II CCD diffractometer using
ꢀ
graphite-monochromated Mo K
a
radiation (
l
¼ 0.71073 A) at 295 K.
Data collection and reduction were performed using the SAINT
software [26]. An empirical absorption correction was applied
using the SADABS program [27]. The structures were solved by
direct methods using a SIR-2004 software and refined by full-
matrix least-squares based on F2 with anisotropic thermal param-
eters for all non-hydrogen using SHELXTL package of programs
[28,29]. All H atoms in 1e10 were placed at geometrically idealized
positions and subsequently treated as riding atoms, with
44.75; H, 2.17; found: C, 44.83; H, 2.25. IR (KBr disk):
n(C^O) 2060
(vs), 2000 (s), 1953 (s), 1918 (s) cmꢀ1 1H NMR (500 MHz, CDCl3,
.
TMS): 3.28 (s, 1H, CHS), 7.39e7.45 (m, 5H, C6H5), 7.48e7.52 (m, 5H,
C6H5) ppm. 31P NMR (202.5 MHz, CDCl3, 85% H3PO4): 2.74 (s) ppm.
1
13C NMR (125.8 MHz, CDCl3, TMS): 38.5 (d, JCeP ¼ 22 Hz, PCS),
128.8 (s), 130.2 (d, JCeP ¼ 10 Hz), 130.6 (s), 131.2 (d, JCeP ¼ 9 Hz),
ꢀ
CeH ¼ 0.93 (aromatic), 0.97 (CH2) and 0.96 (CH3) A and Uiso(H)
131.9 (s), 132.4 (s), 138.9 (s), 139.2 (s) (2C6H5), 209.9 (br, C^O),
2
values of 1.2Ueq(C) or 1.5Ueq(Cmethyl). Ortep plots of complexes are
drawn using a WinGX software [30]. Details of crystal data, data
collections, and structure refinements are summarized in Table 1
for 1e5 and Table 2 for 6e10.
211.6 (d, JCeP ¼ 5.6 Hz, C^O) ppm. Anal. Calcd for C31H19ClFe2
-
NO5PS2 (9): C, 51.16; H, 2.63; found: C, 51.14; H, 2.37. IR (KBr disk):
n
(C^O) 2040 (s), 1973 (vs), 1909 (s), n .
(C]N) 1575 (w) cmꢀ1 1H
NMR (500 MHz, CDCl3, TMS): 6.51e7.13, 7.14e7.48 (2m,19H, C6H4Cl,
3C6H5) ppm. 31P NMR (202.5 MHz, CDCl3, 85% H3PO4): 37.79
(s) ppm. 13C NMR (125.8 MHz, CDCl3, TMS): 128.2 (s), 128.5 (s),
128.7 (s), 128.9 (s), 129.0 (s), 130.2 (s), 130.4 (d, JCeP ¼ 7.3 Hz), 130.6
(s), 131.6 (s), 132.4 (d, JCeP ¼ 7.4 Hz), 151.0 (s) (C6H4Cl, 3C6H5), 138.4
3. Results and discussion
3.1. Syntheses of complexes
(d, 1JCeP ¼ 26.2 Hz, PCS2), 185.0 (s, C]N), 211.0, 212.9 (s, s, Fe(CO)2),
2
219.2 (d, JCeP ¼ 14 Hz, Fe(CO)3) ppm. Anal. Calcd for C31H19ClFe2
Mixture of [NEt4][Ph2PCS2] and Fe3(CO)12 in THF is stirred for 1 h
at room temperature to give a red-brown solution. The solution
-
NO5PS2 (10): C, 51.16; H, 2.63; found: C, 51.28; H, 2.51. IR (KBr disk):
Table 1
Crystal data and structure refinements for 1e5.
1
2
3
4
5
Formula
Mr
C20H13Fe2O6PS2
556.11
C26H17Fe2O6PS2
632.21
C21H13Fe2O7PS2
584.12
C26H15Fe2O7PS2
646.19
C43H30Fe2O6P2S2
880.45
Cryst system
Space group
Triclinic
P ꢀ1
Triclinic
P ꢀ1
Monoclinic
P 21/n
12.918(2)
11.8932(18)
16.356(3)
90
105.8171(17)
90
2417.7(7)
4
Monoclinic
P 21/n
12.475(3)
13.498(2)
15.964(3)
90
94.992(2)
90
2677.9(9)
4
Triclinic
P ꢀ1
ꢀ
a/A
9.9421(18)
10.4192(19)
11.092(3)
87.305(2)
89.6091(15)
87.560(2)
1146.7(4)
2
11.1287(13)
11.6523(13)
12.1381(14)
91.9176(14)
94.6305(14)
117.2066(13)
1390.9(3)
2
10.723(3)
10.735(2)
19.179(3)
102.225(2)
98.224(3)
107.692(2)
2004.0(7)
2
ꢀ
b/A
ꢀ
c/A
ꢁ
ꢁ
a
/
b
/
ꢁ
g
/
3
ꢀ
V/A
Z
Dc/g cmꢀ3
1.611
1.550
1.510
1.288
1.605
1.478
1.603
1.343
1.459
0.955
m
/mmꢀ1
F(000)
560
640
1176
1304
900
Index ranges
ꢀ12 ꢂ h ꢂ 12
ꢀ13 ꢂ kk ꢂ 13
ꢀ12 ꢂ l ꢂ 14
10,153
ꢀ14 ꢂ h ꢂ 13
ꢀ15 ꢂ k ꢂ 15
ꢀ15 ꢂ l ꢂ 15
12,232
ꢀ15 ꢂ h ꢂ 16
ꢀ15 ꢂ k ꢂ 15
ꢀ21 ꢂ l ꢂ 21
20,189
ꢀ16 ꢂ h ꢂ 16
ꢀ17 ꢂ k ꢂ 17
ꢀ20 ꢂ l ꢂ 20
12,173
ꢀ13 ꢂ h ꢂ 13
ꢀ13 ꢂ k ꢂ 13
ꢀ24 ꢂ l ꢂ 24
16,403
Reflections measured
Unique reflections
5206
6267
5501
6120
8978
Reflections (I > 2
s
(I))
4516
4845
4595
5571
6840
Rint
0.0245
55.2
0.0231
55.0
0.0530
54.96
0.0431
55.2
0.0593
54.6
ꢁ
2
qmax
/
R
0.0314
0.0328
0.0353
0.0487
0.0624
Rw
0.0955
0.0920
0.0935
0.1507
0.1895
GooF
1.05
0.36/ꢀ0.53
1.02
0.32/ꢀ0.25
1.07
0.38/ꢀ0.32
1.19
0.89/ꢀ0.62
1.02
0.94/ꢀ0.79
ꢀꢀ3
Largest diff peak and hole/e A

42
Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
Table 2
Crystal data and structure refinements for 6e10.
6
7
8
9
10
Formula
Mr
C20H13Fe2O5PS4
604.25
C37H20Fe4O12P2S2
1006.01
C19H11Fe2O6PS
510.02
C31H19ClFe2NO5PS2
727.73
C31H19ClFe2NO5PS2
727.73
Cryst system
Space group
Triclinic
P ꢀ1
Triclinic
P ꢀ1
Monoclinic
P 21/n
9.8617(14)
21.528(3)
10.5326(15)
90
110.929(2)
90
2088.6(5)
4
Monoclinic
P 21/n
12.0960(11)
16.7014(15)
15.2230(14)
90
91.8054(12)
90
3073.8(5)
4
Monoclinic
P 21/c
11.661(2)
13.676(3)
19.634(4)
90
105.088(2)
90
3023.2(10)
4
ꢀ
a/A
10.1895(17)
10.5219(15)
11.788(2)
80.0722(18)
87.9470(14)
78.440(3)
1219.7(3)
2
10.6449(10)
12.5903(12)
16.9996(16)
110.1909(11)
92.0435(12)
109.1531(12)
1991.3(3)
2
ꢀ
b/A
ꢀ
c/A
ꢁ
ꢁ
a
/
b
/
ꢁ
g
/
3
ꢀ
V/A
Z
Dc/g cmꢀ3
1.645
1.626
1.678
1.675
1.622
1.598
1.573
1.260
1.599
1.281
m
/mmꢀ1
F(000)
608
1008
1024
1472
1472
Index ranges
ꢀ13 ꢂ h ꢂ 13
ꢀ13 ꢂ k ꢂ 13
ꢀ15 ꢂ l ꢂ 14
10,765
ꢀ12 ꢂ h ꢂ 13
ꢀ16 ꢂ k ꢂ 16
ꢀ22 ꢂ l ꢂ 21
17,614
ꢀ12 ꢂ h ꢂ 12
ꢀ27 ꢂ k ꢂ 27
ꢀ13 ꢂ l ꢂ 13
18,031
ꢀ15 ꢂ h ꢂ 15
ꢀ20 ꢂ k ꢂ 21
ꢀ19 ꢂ l ꢂ 19
26,613
ꢀ14 ꢂ h ꢂ 14
ꢀ17 ꢂ k ꢂ 17
ꢀ25 ꢂ l ꢂ 25
24,318
Reflections measured
Unique reflections
5509
8991
4797
7106
6644
Reflections (I > 2
s(I))
4260
6757
3529
5356
5197
Rint
0.0274
55.2
0.0291
55.0
0.0394
55.10
0.0343
55.2
0.0411
54.4
ꢁ
2
qmax
/
R
0.0341
0.0364
0.0341
0.0319
0.0434
Rw
0.0951
0.1127
0.0887
0.0862
0.1106
GooF
1.04
0.34/ꢀ0.27
1.02
0.46/ꢀ0.32
1.03
0.44/ꢀ0.34
1.02
0.28/ꢀ0.27
1.08
0.45/ꢀ0.45
ꢀꢀ3
Largest diff peak and hole/e A
reacts in situ with an excess of electrophile E-X such as MeI and
PhCH2Br to afford orange complexes 1 and 2 in yields of 46 and
47%. According to X-ray diffraction analyses of 1 and 2, M1, an
CH3COCl has been carried out. An orange complex 3 has been
obtained in 44% yield. Similarly, PhCOCl as an electrophile
generates an orange complex 4 in 48% yield. Moreover, as an
example, the reaction of 4 with PPh3 in the presence of Me3NO has
been performed to investigate the site of the substitution of PPh3
for a carbonyl group at the Fe(CO)3 moiety in each complex and to
modify the coordination spheres. The orange complex 5 as the
only product has been obtained in almost quantitative yield.
Accordingly the synthesis of 5 provides the method for modifying
the Fe1 coordination sphere via replacing a CO ligand as shown in
Section 3.2.
S-centered anion ([Fe2(CO)6(m
-Ph2PCS2)]ꢀ), is proposed as an
intermediate (Scheme 1). The intermediate, M1, has been charac-
terized not only by in-situ IR spectroscopy in which two strong
absorptions at 1928 and 2014 cmꢀ1 indicate the presence of
terminal carbonyl groups and but also by HR-MS (base peak at
m/z ¼ 541). In order to further confirm M1, the reaction of M1 with
Particularly, M1 reacts with CS2 and then with MeI to produce
a purple complex 6 in 39% yield. Consequently the synthesis of 6
provides the method for modifying the Fe2 coordination sphere as
mentioned in Section 3.2 [12e14,31]. To account for the formation
of 6, a possible pathway has been proposed as follows: first,
nucleophilic attack of M1 at the carbon atom of CS2 results in
(OC)3Fe
Fe(CO)3
S
C
(7)
Ph2P
S
(OC)3Fe
Fe(CO)3
[Fe2(CO)6(
thioacyl ligand by the sulfur lone electron pair with loss of carbon
monoxide forms [Fe2(CO)5(
-Ph2PCSSC(]S)Sꢀ)], finally attack
-Ph2PCSSC(]S)Sꢀ)] at MeI via an SN2 process
m
-Ph2PCSSC(]S)Sꢀ)], then coordination of the dangling
PPh2
2. Ph2P-Cl
m
1. Fe3(CO)12
of [Fe2(CO)5(
m
produces 6.
(OC)3Fe
Ph2P
Fe(CO)3
(OC)3Fe
Fe(CO)3
Since the cluster anion M1 is S-centered, maybe, it
can be expected that the reaction of M1 and Fe3(CO)12 can lead to
Fe3(CO)12
E-X
- X-
-
Ph2PCS2
S
C
(1-4)
C
S
Ph2P
a Seyferthetype intermediate [Fe2(CO)6(m-Ph2PCSS)Fe2(CO)6(m-
CO)]ꢀ. The Seyferthetype intermediate is trapped by Ph2PCl, the
brown complex 7 has been obtained in 35% yield. Indeed, this is very
S-
(M1)
S-E
analogous to that the reaction of the Seyferth intermediate [(
SR)Fe2(CO)6]ꢀ generated from the Fe3(CO)12/RSH/Et3N mixture with
Ph2PCl yields the butterfly complex [( -PPh2)( -SR)Fe2(CO)6]; hence,
exploiting the cluster anion M1 has opened up a new route to
synthesize high-nuclearity Fe/S cluster complexes [7e12,31].
More interestingly, M1 reacts in situ with the electrophile
PhCCl]N(4-C6H4Cl) to produce complexes 8e10 in yields of 11%,
38%, and 13%, respectively (Scheme 2) [11,14,31]. Therefore, the
syntheses of 9 and 10 provide the second method for modifying the
Fe2 coordination sphere as indicated in Section 3.2. 8 is common in
m-CO)(m-
1. CS2
PPh3
2. CH3-I
Fe(CO)2
m
m
(Ph3P)(OC)2Fe
Fe(CO)3
(OC)3Fe
Ph2P
(5)
S
C
S
C
S
Ph2P
S
C
SCH3
S-COPh
(6)
Scheme 1. Syntheses of complexes 1e7 (E ¼ CH3, 1; E ¼ PhCH2, 2; E ¼ CH3CO, 3;
E ¼ PhCO, 4) via the S-centered cluster anion M1.

Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
43
(OC)3Fe
Ph2P
Fe(CO)2
SCPh]N(4-C6H4Cl) group with loss of carbon monoxide generates
10. Obviously, more work is required in order to exhaustively
investigate reactions of the S-centered cluster anion with imidoyl
chlorides. But, syntheses of 9 and 10 show that a new organome-
tallic rearrangement reaction has been discovered [23e25].
S
S
C
(10)
ArN
Fe(CO)2
Ph
(OC)3Fe
Ph2P
(OC)3Fe
Ph2P
Fe(CO)3
Fe3(CO)12
PhC(Cl)=NAr
-
Ph2PCS2
NAr
S
C
(9)
(8)
C
S
3.2. X-ray structures of complexes
S-
S
(M1)
Ph
Fortunately, structures of all novel complexes have been deter-
mined by X-ray crystallography. Selected geometric parameters
have been listed in Table 3 (for 1e5) and 4 (for 6e10). As shown in
(OC)3Fe
Ph2P
Fe(CO)3
C
S
Figs.1e4, products formulated as Fe2(CO)6(
m
-Ph2PCSSE) (E ¼ CH3,1;
H
E ¼ CH2Ph, 2; E ¼ COCH3, 3; E ¼ COPh, 4) are chiral, with two Fe
atoms having different coordinating environments, namely for each
complex two Fe(CO)3 moieties are not chemically equivalent. Five
atoms (Fe1Fe2S1P1C7) form an irregular polyhedron. The Fe1eFe2
Scheme 2. Syntheses of complexes 8e10 via the cluster-sulfido anion M1 (Ar ¼ 4-
C6H4Cl).
ꢀ
bond distance (2.6569(5)e2.6369(6) A) lies within the range
ꢀ
(OC)3Fe
Ph2P
Fe(CO)2
(OC)3Fe
Ph2P
Fe(CO)3
previously noted for single bonds (2.43e2.88 A) but is longer than
ꢀ
those observed (2.618(1)e2.627(1) A) in the dithioester complexes
S coordination
S
S
S
S
C
C
[32,33]. Unlike those of
m-SR diiron complexes, the S1 atom bridges
the two Fe atoms asymmetrically, with FeeS distances
ArN
(10)
ArN
SNi
ꢀ
ꢀ
Ph
2.1858(6)e2.1810(6) A for Fe2eS1 and 2.2883(7)e2.2816(7) A for
Fe1eS1. The bond distances of C7eS1 and C20eS2 in the regions
Ph
ꢀ
ꢀ
1.809(2)e1.783(2) A and 1.817(2)e1.786(3) A are close to the typical
ꢀ
CeS single-bond length of 1.81 A [21]. Moreover, the C7eFe2 bond
distance of 2.065(2)e2.044(2) A is consistent with a single bond,
(OC)3Fe
Ph2P
Fe(CO)2
N-Ar
(OC)3Fe
Ph2P
Fe(CO)3
S
ꢀ
(M1)
N coordination
PhC(Cl)=NAr
S
because the typical CeFe single-bond length is within the range
C
C
ꢀ
2.0e2.2 A [34]. Thus, the carbon atom in the Ph2PCSSE ligand is an
S
S-C(Ph)=NAr
sp3 hybridization and links one Fe atom by a covalent bond, the
phosphorus atom of the Ph2PCS moiety binds the other Fe atom by
a dative bond whereas the sulfur atom bridges two metals by
a covalent bond and a dative bond; the doubly bridging-chelating
ligands each act as six-electron donors, giving each metal an
18-electron configuration and a quasioctahedral geometry, in which
three of the coordination sites are occupied by terminal carbonyl
groups. To our knowledge, this bonding mode of the ligand
Ph2PCSSE is unprecedented [18e21].
Ph
(9)
Scheme 3. Possible pathway to complexes 9 and 10 via the S-centered cluster anion
M1.
the reactions of M1 with imidoyl chlorides. However, at the present
stage, the formation of 8 is difficult to explain although M1 in the
presence of protic acid such as CF3CO2H generates 8 (12 mg of 8
from 1 mmol Fe3(CO)12). A possible mechanistic scheme accounting
for the formation of 9 and 10 is proposed in Scheme 3. The first step
involves nucleophilic attack of an S-centered anion at the imino
carbon with concomitant elimination of chloride ion, resulting
An X-ray diffraction analysis on 5 (Fig. 5) indicates that the
ligand Ph2PC(S)SCOPh remains intact and its bonding mode is the
same as in 4 (viz. a m
-k2P,C:k2S pattern). In 5, the Fe1eFe2 bond
ꢀ
distance is 2.6536(7) A, PPh2 and PPh3 are cis to each other with
a 98.39(3)ꢁ angle of P1eFe1eP2.
in Fe2(CO)6(m-Ph2PC(S)SCPh]N(4-C6H4Cl)); subsequent coordina-
tion of the dangling iminoacyl ligand by the nitrogen lone electron
pair with loss of carbon monoxide produces 9. On the other hand,
after attack of the N atom at the carbon atom of the CS2 group
with cleavage of the CeS bond between Ph2PCS and SCPh units
(SNi, i.e. intramolecular nucleophilic substitution), coordination of
the S atom of the N(4-C6H4Cl)CPh]S group resulted from the
Interestingly, an X-ray diffraction study reveals that there is the
unprecedented ligand Ph2PCSSC(]S)SMe in 6 as shown in Fig. 6.
The bonding mode of the Ph2PCS group is similar to the above
complexes whereas the thiocarbonyl S atom as a two-electron
donor substitutes one carbonyl group of the Fe(CO)3 moiety with
an 156.63(3)ꢁ angle of S3eFe2eFe1 to form Fe2(CO)5 complex 6,
Table 3
Selected geometric parameters (A, ꢁ) for 1e5.
ꢀ
1
2
3
4
5
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC7
S1eC7
S2eC7
Fe2eC7
S2eC20
2.6523(6)
2.2474(6)
2.2830(7)
2.1844(7)
1.802(2)
1.806(2)
1.764(2)
2.047(2)
1.786(3)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC7
S1eC7
S2eC7
Fe2eC7
C20eS2
2.6569(5)
2.2429(7)
2.2883(7)
2.1810(6)
1.796(2)
1.809(2)
1.765(2)
2.044(2)
1.817(2)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC7
S1eC7
S2eC7
Fe2eC7
C20eS2
2.6479(5)
2.2503(7)
2.2824(7)
2.1836(7)
1.787(2)
1.787(2)
1.768(2)
2.060(2)
1.799(3)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC7
S1eC7
S2eC7
Fe2eC7
S2eC20
2.6369(6)
2.2528(7)
2.2816(7)
2.1858(6)
1.800(2)
1.783(2)
1.768(2)
2.065(2)
1.798(2)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC6
S1eC6
S2eC6
Fe2eC6
S2eC19
2.6536(7)
2.2765(9)
2.2828(10)
2.1929(10)
1.809(3)
1.792(3)
1.782(3)
2.036(3)
1.806(4)
P1eFe1eC1
Fe1eS1eFe2
S2eC7eS1
95.28(8)
72.80(2)
121.31(11)
P1eFe1eC1
Fe1eS1eFe2
S2eC7eS1
94.42(9)
72.90(2)
122.32(11)
P1eFe1-C1
Fe1eS1eFe2
S2eC7eS1
97.40(9)
72.69(2)
121.84(12)
P1eFe1eC1
Fe1eS1eFe2
S2eC7eS1
93.30(7)
72.31(2)
121.69(12)
P1eFe1eP2
Fe1eS1eFe2
S2eC6eS1
98.39(3)
72.70(3)
117.40(18)

44
Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
Table 4
Selected geometric parameters (A, ꢁ) for 6e10.
ꢀ
6
7
8
9
10
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
Fe2eS3
P1eC6
2.6777(7)
2.2572(8)
2.2833(8)
2.1969(8)
2.2292(9)
1.778(2)
1.822(2)
1.772(3)
2.001(2)
1.733(3)
1.661(3)
1.730(3)
1.793(3)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
Fe3eFe4
Fe3eP2
Fe4eP2
Fe3eS2
Fe4eS2
P1eC7
2.6299(6)
2.2471(8)
2.2962(9)
2.1865(9)
2.5732(6)
2.2206(8)
2.2412(9)
2.2803(8)
2.2767(8)
1.799(3)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC7
2.6686(6)
2.2495(7)
2.2797(9)
2.1829(9)
1.771(3)
1.783(3)
2.045(3)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
P1eC6
2.6505(5)
2.2683(7)
2.2832(6)
2.2080(6)
1.782(2)
1.803(2)
1.773(2)
1.9896(17)
1.995(2)
1.299(3)
1.753(2)
1.488(3)
1.447(3)
Fe1eFe2
Fe1eP1
Fe1eS1
Fe2eS1
Fe2eS2
P1eC6
2.6399(8)
2.2567(10)
2.2776(10)
2.2123(10)
2.2168(11)
1.789(3)
1.810(3)
1.981(3)
1.439(4)
1.345(4)
S1eC7
Fe2eC7
S1eC6
S2eC6
S1eC6
S2eC6
S1eC6
Fe2eN1
Fe2eC6
N1eC19
S2eC19
C19eC20
N1eC26
Fe2eC6
N1eC6
N1eC19
S2eC19
C19eC20
N1eC26
Fe2eC6
S2eC19
S3eC19
S4eC19
S4eC20
S1eC7
S2eC7
Fe2eC7
1.795(3)
1.792(3)
2.050(3)
1.674(3)
1.487(4)
1.447(4)
S3eFe2eFe1
Fe1eS1eFe2
S1eC6eS2
156.63(3)
73.38(2)
120.17(13)
Fe3eS2eFe4
Fe1eS1eFe2
S1eC7eS2
68.76(2)
71.79(3)
128.40(16)
Fe2eS1eC7
Fe1eS1eFe2
Fe2eC7eS1
61.11(9)
73.42(3)
69.14(9)
Fe1eFe2eN1
Fe1eS1eFe2
S1eC6eS2
153.94(5)
72.31(2)
119.35(12)
Fe1eFe2eS2
Fe1eS1eFe2
N1eC6eS1
153.52(3)
72.01(3)
118.1(2)
namely the ligand acts as an eight-electron donor in a
kS fashion. The Fe1eFe2 bond distance (2.6777(7) A) is slightly
longer than those of 1e5. The C19eS3 bond distance of 1.661(3) A
m
-k2P,C:k2S-
donor is coordinated to the Fe2(CO)6 unit in a
m
-k2P,C:k2S pattern.
ꢀ
ꢀ
The Fe1eFe2 bond distance (2.6686(6) A) is close to that of 6. As
indicated in Fig. 9 and 10, 9 and 10 are isomers, each contains an
ꢀ
ꢀ
ꢀ
indicates the presence of the above-mentioned thiocarbonyl group
ironeiron single bond (2.6505(5) A for 9 and 2.6399(8) A for 10) with
three terminal carbonyl ligands on Fe1 and two on Fe2. Isomeric
ligands Ph2PCSSCPh]N(4-C6H4Cl) and Ph2PCSN(4-C6H4Cl)CPh]S
each are eight-electron donors, namely each Ph2PCS group acts as
a six-electron donor, the N atom of the imine CPh]N(4-C6H4Cl) group
ꢀ
whereas the C6eS1 bond distance of 1.822(2) A represents
a normal CeS single bond.
As shown in Fig. 7, the three-electron PPh2 group replaces the
bridging carbonyl group in the Seyferthetype intermediate to give
bis(Fe2(CO)6) complex 7. 7 is also chiral, two Fe2(CO)6 units are not
chemically equivalent. In fact, as can be seen from Table 4, the
measured geometric parameters indicate that four [Fe(CO)3]
moieties in 7 each are not chemically equivalent. The Fe3eFe4 bond
affords two electrons to form Fe2(CO)5 complex 9 (in a
mode) whereas the S atom of the thioacyl PhC]S group gives two
electrons toresult in Fe2(CO)5 complex 10 (in a
-k2P,C:k2S-kS fashion).
m
-k2P,C:k2S-kN
m
ꢀ
In 9, the Fe2eN1 bond distance is 1.9896(17) A and the bond angle
distance (2.5732(6) A) is slightly shorter than that of the Fe1eFe2
of Fe1eFe2eN1 is 153.94(5)ꢁ. By contrast, in 10, the Fe2eS2 bonꢁd
ꢀ
ꢀ
ꢀ
bond (2.6299(6) A). As in 1e6, the Ph2PCS group in 7 has the
distance is 2.2168(11) A, the bond angle of Fe1eFe2eS2 is 153.52(3) .
ꢀ
same mode coordinating to the Fe1 and Fe2 centers. The angle of
P2/S2eC7 ¼ 171.50(10)ꢁ reveals that the Fe1Fe2S1P1C7 cluster
core is linked to a butterfly Fe3Fe4S2P2 cluster core via a C7eS2
equatorial bond, viz. 7 is an e-type isomer [7,12e14,31].
More interestingly, as can be seen in Fig. 8, 8has the unprecedented
ligand Ph2PCHS (vide infra). The ligand Ph2PCHS as a six-electron
The C19eS2 bond distance of 1.674(3) A indicates the existence
of the above-mentioned thiocarbonyl group. The heterocyclic
five-membered ring for C6Fe2N1C19S2 in 9 is essentially planar.
Similarly, the heterocyclic five-membered ring for C6Fe2S2C19N1 in
10 is coplanar.
3.3. Spectroscopies of complexes
All novel complexes described above have also been character-
ized by elemental analyses and spectroscopies. As indicated in
Fig. 1. X-ray crystal structure with atom-numbering scheme for 1. Displacement
Fig. 2. X-ray crystal structure with atom-numbering scheme for 2. Displacement
ellipsoids are drawn at the 30% probability level.
ellipsoids are drawn at the 30% probability level.

Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
45
Fig. 5. X-ray crystal structure with atom-numbering scheme for 5. Displacement
ellipsoids are drawn at the 30% probability level.
Fig. 3. X-ray crystal structure with atom-numbering scheme for 3. Displacement
ellipsoids are drawn at the 30% probability level.
Figs. 1e10, their IR spectra (Tables 5 and 6) show characteristic
absorption bands in the region 2069e1909 cmꢀ1 for their terminal
CO ligands. Additionally the ester group appears at 1711 cmꢀ1 for 3,
1678 cmꢀ1 for 4 and 1685 cmꢀ1 for 5. Interestingly, the 1H NMR
spectra (Tables 7 and 8) exhibit a singlet due to the Me group at
1.69 ppm for 1 and at 1.99 ppm for 3 whereas the Me group of 6
shows a singlet at 2.84 ppm. The 1H NMR spectrum of 2 exhibits one
AB quartet at 3.09 and 3.45 ppm due to coupling between the two
Fig. 6. X-ray crystal structure with atom-numbering scheme for 6. Displacement
ellipsoids are drawn at the 30% probability level.
Fig. 4. X-ray crystal structure with atom-numbering scheme for 4. Displacement
Fig. 7. X-ray crystal structure with atom-numbering scheme for 7. Displacement
ellipsoids are drawn at the 30% probability level.
ellipsoids are drawn at the 20% probability level.

46
Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
Fig. 8. X-ray crystal structure with atom-numbering scheme for 8. Displacement
ellipsoids are drawn at the 30% probability level.
Fig. 10. X-ray crystal structure with atom-numbering scheme for 10. Displacement
ellipsoids are drawn at the 30% probability level.
magnetically nonequivalent protons of the CH2 group. For 8, the CHS
group as a singlet appears at 3.28 ppm. In addition, the 1H NMR
spectra of all complexes display the corresponding signals for their
phenyl groups. The 31P{1H} NMR spectra (Tables 9 and 10) show
a singlet at 37.01 ppm for 1, 37.26 ppm for 2, 36.91 ppm for 3,
37.55 ppm for 4, 36.29 ppm for 6, 37.79 ppm for 9 and 46.55 ppm for
10 whereas a singlet appears at 2.74 ppm for 8 (vide supra). The 31P
NMR spectrum of 5 displays two doublets at 40.13 and 59.88 ppm
Table 5
IR data (cmꢀ1) for 1e5.
1
2
3
4
5
n
(C^O)
(C]O)
2062 (vs),
2000 (vs),
1973 (vs)
2064 (vs),
2045 (s),
2022 (s),
1982 (s)
2064 (vs),
2019 (s),
1994 (s),
1969 (s),
1949 (s)
1711 (m)
2066 (vs),
1986 (vs),
1954 (vs)
2034 (vs),
1980 (vs),
1922 (vs)
2
n
1678 (m)
1685 (m)
which are attributable to PPh2 and PPh3 with a JPeP coupling
constant of 51.0 Hz. The 31P NMR spectrum of 7 shows two singlets at
42.07 and 142.45 ppm which are due to Ph2P and bridging Ph2P
groups, respectively. Clearly, the 31P NMR data are in agreement with
their X-ray diffraction analyses. In the 13C{1H} NMR spectra (Table
11), 1e5 each shows the only singlet at ca. 210 ppm corresponding
to terminal carbonyl C atoms, suggesting that the carbonyl ligands
are undergoing rapid exchange between two Fe atoms on the NMR
Table 6
IR data (cmꢀ1) for 6e10.
6
7
8
9
10
n
(C^O)
(C]N)
2044 (vs),
1979 (vs),
1921 (vs)
2061 (vs),
2022 (vs),
1996 (vs),
1966 (vs)
2060 (vs),
2000 (s),
1953 (s),
1918 (s)
2040 (s),
1973 (vs),
1909 (s)
2035 (vs),
1979 (s),
1920 (s)
n
1575 (w)
time scale at room temperature [5,17,35]. Terminal carbonyl and
thiocarbonyl C atoms of 6 as five singlets appear in the region
210.7e223.8 ppm, while 7 exhibits two singlets at 206.0 and
213.7 ppm which are due to two different Fe2(CO)6 units. 8 displays
one broad singlet at 209.9 ppm and one doublet at 211.6 ppm
(2JCeP
¼
5.6 Hz) while 9 shows two singlets at 211.0 and
212.9 ppm assignable to the Fe(CO)2 group and one doublet at
Table 7
1H NMR data (ppm) for 1e5.
1
2
3
4
5
1.69
3.09, 3.45
1.99 (s, 3H,
CH3),
7.25e7.59
(m, 10H,
2C6H5)
7.32e7.69
(3m, 15H,
3C6H5)
7.13e7.69
(5m, 30H,
6C6H5)
2
(s, 3H, CH3),
7.36e7.92
(5m, 10H,
2C6H5)
(dd, JHeH ¼ 11.9 Hz,
2H, CH2),
6.94e7.99 (4m, 15H,
3C6H5)
Fig. 9. X-ray crystal structure with atom-numbering scheme for 9. Displacement
ellipsoids are drawn at the 30% probability level.

Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
47
Table 8
and the C]N group appears as a singlet at 185.0 ppm. The PCS group
displays a doublet at 134.2 ppm (1JCeP ¼ 17.4 Hz) and the C]S group
a singlet at 202.5 ppm for 10. From the above discussion, it should be
apparent that except for fluxionality of CO site-exchanges in their
solutions, spectroscopic data are in accordance with X-ray diffraction
analyses [5,17,35].
1H NMR data (ppm) for 6e10.
6
7
8
9
10
2.84
7.15e7.89
(5m, 4C6H5)
3.28
(s, CHS)
7.39e7.52
(2m, 2C6H5)
6.51e7.48
(2m, C6H4Cl,
3C6H5)
7.05e7.50
(2m, C6H4Cl,
3C6H5)
(s, CH3),
7.45e7.59
(2m, 2C6H5)
4. Conclusion
Table 9
31P NMR data (ppm) for 1e5.
A novel type of cluster salt [NEt4][Fe2(CO)6(m-Ph2PCS2)] ([NEt4]
[M1]) has been prepared via the new reaction of the heteroallyl
anion salt [NEt4][Ph2PCS2] and Fe3(CO)12. Reactions of [NEt4][M1]
with a series of electrophiles have led to the syntheses of novel Fe/S
clusters 1e10 successfully. More importantly, the structures
of these novel complexes have been unambiguously determined
by X-ray crystallography. 9 and 10 are isomers, displaying that
a new organometallic rearrangement has been found. Detailed
mechanisms for the novel reactions and other interesting applica-
tions of the S-centered cluster anion M1 and its extended type
1
2
3
4
5
2
37.01
37.26
36.91
37.55
40.13 (d, JPeP ¼ 51.0 Hz, PPh2),
2
59.88 (d, JPeP ¼ 51.0 Hz, PPh3)
Table 10
31P NMR data (ppm) for 6e10.
6
7
8
9
10
[m
-(GeCYeZ)Fe2(CO)6]ꢀ (G ¼ potential donor group; Y ¼ S, Se;
36.29
42.07, 142.45
2.74
37.79
46.55
Z ¼ S, Se, NR, CHR) in the syntheses of cluster complexes are under
investigation.
219.2 ppm attributable to the Fe(CO)3 group (2JCeP ¼ 14 Hz). As with
9, 10 shows two singlets at 211.5 and 215.2 ppm due to the Fe(CO)2
group and one doublet at 217.6 ppm attributable to coupling
between the Ph2P group and terminal carbonyl C atoms of the
Fe(CO)3 group (2JCeP ¼ 14 Hz). The above facts indicate that for each
of 8e10 there is no carbonyl exchange process between two Fe(CO)3
groups or between Fe(CO)2 and Fe(CO)3 groups but within the
Fe(CO)3 group the carbonyl ligands are undergoing rapid exchange
on the NMR time scale at room temperature (Table 12) [5,17,35]. It is
worth noting that in the 13C{1H} NMR spectra the PCS2 group
appears as a doublet at 136.7 ppm (1JCeP ¼ 23.3 Hz) for 1, 136.8 ppm
(1JCeP ¼ 23.1 Hz) for 2, 134.9 ppm (1JCeP ¼ 26.5 Hz) for 3, 134.9 ppm
(1JCeP ¼ 26.7 Hz) for 4, 136.4 ppm (1JCeP ¼ 50.0 Hz) for 5,
138.0 ppm (1JCeP ¼ 26.4 Hz) for 6, 134.4 ppm (1JCeP ¼ 30.4 Hz) for 7
while the PCHS group as a doublet at 38.5 ppm (1JCeP ¼ 22 Hz) for 8.
For 9, the PCS2 group shows a doublet at 138.4 ppm (1JCeP ¼ 26.2 Hz)
Acknowledgments
We are grateful to the Natural Science Foundation of China (No.
20572091), Project Funded by the Priority Academic Program
Development of Jiangsu Higher Education Institutions (PAPD), Mao
Zedong Foundation of China and Natural Science Foundation of
Jiangsu Province (No. 05KJB150151) for financial support of this
work.
Appendix A. Supplementary material
CCDC 859503e859512 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
Table 11
13C NMR data (ppm) for 1e5.
1
2
3
4
5
21.6 (CH3), 128.7
43.33 (CH3),
29.0 (CH3), 128.0
127.1, 128.1
128.6, 129.6
(d, J ¼ 2.4 Hz), 128.8
(d, J ¼ 4.0 Hz), 131.4
(d, J ¼ 2.5 Hz), 131.6,
131.9 (d, J ¼ 1.9 Hz),
132.0, 132.4 (d, J ¼ 9.6 Hz),
132.5 (d, J ¼ 8.9 Hz)(2C6H5),
127.2, 128.4,
(d, J ¼ 9.3 Hz), 128.4
(d, J ¼ 9.9 Hz), 128.6
(d, J ¼ 9.1 Hz), 128.7,
131.1, 131.7, 132.2
(d, J ¼ 9.3 Hz), 133.0
(d, J ¼ 10.2 Hz), 133.5,
135.7 (2C6H5), 134.9
(d, J ¼ 12.6 Hz), 130.3
(d, J ¼ 12.6 Hz), 130.7,
132.0, 132.3, 133.2, 134.5
(d, J ¼ 12.6 Hz), 134.65
(d, J ¼ 12.6 Hz), 135.2
(d, J ¼ 12.6 Hz), 135.4 (5C6H5),
128.9 (d, J ¼ 9.9 Hz),
131.6, 131.9, 132.6
(d, J ¼ 8.1 Hz), 136.3 (2C6H5),
(d, J ¼ 10.2 Hz), 131.2,
131.7, 132.2 (d, J ¼ 8.7 Hz),
133.1 (d, J ¼ 9.7 Hz) (2C6H5),
1
1
136.8 (d, JCeP ¼ 23.1 Hz,
134.9 (d, JCeP ¼ 26.5 Hz, PCS2),
PCS2), 210.3 (6C^O)
192.3 (C]O), 210.4 (6C^O)
1
1
1
136.7 (d, JCeP ¼ 23.3 Hz, PCS2),
(d, JCeP ¼ 26.7 Hz, PCS2),
136.4 (d, JCeP ¼ 50.0 Hz, PCS2),
210.4(C^O)
188.7 (C]O), 210.5 (C^O)
189.6 (C]O), 207.0 (C^O)
Table 12
13C NMR data (ppm) for 6e10.
6
7
8
9
10
1
21.76 (CH3), 128.7
128.7, 128.8, 129.6,
129.8, 129.9, 130.5,
130.8, 130.9, 131.6,
131.7, 131.8, 132.2,
133.1 (4C6H5), 134.4
38.5 (d, JCeP ¼ 22 Hz, PCS),
128.2, 128.5, 128.7,
128.9, 129.0, 130.2,
127.4, 127.8, 127.9, 128.2
(d, J ¼ 9.8 Hz), 129.0
(d, J ¼ 8.8 Hz), 130.7
(d, J ¼ 8.8 Hz), 131.0,
131.7, 132.3 (d, J ¼ 9.1 Hz)
(2C6H5), 138.0
128.8, 130.2 (d, JCeP ¼ 10 Hz),
130.6, 131.2 (d, JCeP ¼ 9 Hz),
131.9, 132.4, 138.9, 139.2
(2C6H5), 209.9 (br, C^O),
(d, JCeP ¼ 9 Hz), 128.5
130.4 (d, JCeP ¼ 7.3 Hz),
(d, JCeP ¼ 10 Hz), 130.1,
130.6, 131.6, 132.4
130.3, 131.1, 132.0 (d, JCeP ¼ 9.2 Hz),
132.3 (d, JCeP ¼ 9.6 Hz), 133.9, 136.2,
139.2, 151.0 (C6H4Cl, 3C6H5), 134.2
(d, JCeP ¼ 7.4 Hz), 151.0
(C6H4Cl, 3C6H5), 138.4
1
2
(d, JCeP ¼ 30.4 Hz, PCS2),
211.6 (d, JCeP ¼ 5.6 Hz, C^O)
1
1
1
(d, JCeP ¼ 26.4 Hz, PCS2),
206.0, 213.7 (C^O)
(d, JCeP ¼ 26.2 Hz, PCS2),
(d, JCeP ¼ 17.4 Hz, PCS), 202.5 (C]S),
210.7, 214.0, 217.3, 217.4,
185.0 (s, C]N), 211.0, 212.9
211.5, 215.2 (s, s, Fe(CO)2), 217.6
2
223.8 (C]S, C^O)
(s, s, Fe(CO)2), 219.2
(d, JCeP ¼ 14 Hz, Fe(CO)3))
2
(d, JCeP ¼ 14 Hz, Fe(CO)3)

48
Y.-C. Shi et al. / Journal of Organometallic Chemistry 716 (2012) 39e48
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