Synthesis and characterization of starlike complexes containing three terminal butterfly Fe/S cluster cores generated via reactions of the three-μ-CO-containing trianions {[(μ-CO)Fe2(CO) 6]3[(μ-SCH2CH2</sub

Article abstract of DOI:10.1021/om050333a

The novel three-μ-CO-containing trianions {[(μ-CO)Fe ₂(CO)₆]₃[(μ-SCH₂ CH ₂)₃N]}^3- (4A) and {[(μ-CO)Fe ₂(CO)₆]₃[1,3,5-(μ-SCH₂) ₃

Full text of DOI:10.1021/om050333a

3764
Organometallics 2005, 24, 3764-3771
Synthesis and Characterization of Starlike Complexes
Containing Three Terminal Butterfly Fe/S Cluster Cores
Generated via Reactions of the Three-µ-CO-Containing
Trianions {[(µ-CO)Fe2(CO)6]3[(µ-SCH2CH2)3N]}3- and
{[(µ-CO)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3]}3- with
Electrophiles
Li-Cheng Song,* Jia Cheng, Feng-Hua Gong, Qing-Mei Hu, and Jing Yan
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai
University, Tianjin 300071, People’s Republic of China
Received April 28, 2005
The novel three-µ-CO-containing trianions {[(µ-CO)Fe2(CO)6]3[(µ-SCH2 CH2)3N]}3- (4A)
and {[(µ-CO)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3]}3- (4B) were prepared by reaction of trithiol
N(CH2CH2SH)3 or 1,3,5-(HSCH2)3C6H3 with Fe3(CO)12 and Et3N in 1:3:3 molar ratio in
THF at room temperature. Further in situ treatment of 4A with electrophiles Ph2PCl,
PhSBr, PhC(Cl)dNPh, and CH2dCHCH2Br afforded starlike complexes [(µ-Y)Fe2(CO)6]3-
[(µ-SCH2CH2)3N] (5-8: Y ) Ph2P, PhS, PhCdNPh, CH2dCHCH2), whereas its reaction with
CS2 followed by treatment with organic halides RX produced complexes [(µ-Y)Fe2(CO)6]3-
[(µ-SCH2CH2)3N] (9-11: Y ) MeSCdS, PhCH2SCdS, CH2dCHCH2SCdS). Similarly, 4B
reacted in situ with Ph2PCl, PhSBr, PhC(Cl)dNPh, CH2dCHCH2Br, and PhNCS to
give starlike complexes [(µ-Y)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3] (12-16: Y ) Ph2P, PhS,
PhCdNPh, CH2dCHCH2, PhNHCdS), whereas its reaction with CS2 followed by treatment
with RX yielded complexes [(µ-Y)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3] (17-19: Y ) MeSCdS,
PhCH2SCdS, CH2dCHCH2SCdS). All the starlike complexes 5-19 contain three terminal
butterfly Fe/S cluster cores, which have been fully characterized by elemental analysis and
spectroscopy, and particularly by X-ray diffraction techniques for 5, 12, 15, and 17.
Scheme 1
Introduction
Iron-sulfur cluster complexes have attracted a great
deal of attention because of their unique structures and
novel chemical reactivities,1 and particularly their
practical applications such as the use as biomimetic
models for the active sites of nitrogenase2 and the Fe-
only hydrogenase.3 Among such cluster complexes
the µ-CO-containing butterfly Fe/S cluster anions
(µ-CO)(µ-RS)Fe2(CO)6 (1), (µ-CO)(µ-RS)[Fe2(CO)6]2-
(µ4-S) (2), and [(µ-CO)Fe2(CO)6]2(µ-SZS-µ) (3) (Scheme
1) are of interest in terms of their ready availability and
high nucleophilicity toward diverse electrophiles.4-6
While the one-µ-CO-containing single-butterfly monoan-
ion 1 was first prepared by Seyferth’s group in 1985
through reaction of Fe3(CO)12 with mercaptan RSH in
* To whom correspondence should be addressed. Fax:
0086-22-23504853. E-mail: lcsong@nankai.edu.cn.
(1) (a) Ogino, H.; Inomata, S.; Tobita, H. Chem. Rev. 1998, 98, 2093.
(b) Song, L.-C. In Trends in Organometallic Chemistry; Atwood, J. L.,
Corriu, R., Cowley, A. H., Lappert, M. F., Nakamura, A., Pereyre, M.,
Eds.; Research Trends: Trivandrum, India, 1999; Vol. 3, p 1. (c) Song,
L.-C. Acc. Chem. Res. 2005, 38, 21.
(4) For single-butterfly, one-µ-CO-containing monoanion 1, see for
example: (a) Seyferth, D.; Womack, G. B.; Dewan, J. C. Organo-
metallics 1985, 4, 398. (b) Seyferth, D.; Hoke, J. B.; Dewan, J. C.
Organometallics 1987, 6, 895. (c) Seyferth, D.; Ruschke, D. P.; Davis,
W. M.; Cowie, M.; Hunter, A. D. Organometallics 1994, 13, 3834.
(d) Delgado, E.; Herna´ndez, E.; Rossell, O.; Seco, M.; Puebla, E. G.;
Ruiz, C. J. Organomet. Chem. 1993, 455, 177. (e) Song, L.-C.; Hu,
Q.-M. J. Organomet. Chem. 1991, 414, 219. (f) Song, L.-C.; Yan, C.-G.;
Hu, Q.-M.; Wang, R.-J.; Mak, T. C. W.; Huang, X.-Y. Organometallics
1996, 15, 1535. (g) Song, L.-C.; Fan, H.-T.; Hu, Q.-M.; Qin, X.-D.; Zhu,
W.-F.; Chen, Y.; Sun, J. Organometallics 1998, 17, 3454. (h) Song,
L.-C.; Lu, G.-L.; Hu, Q.-M.; Fan, H.-T.; Chen, Y.; Sun, J. Organo-
metallics 1999, 18, 3258. (i) Song, L.-C.; Lu, G.-L.; Hu, Q.-M.; Sun, J.
Organometallics 1999, 18, 2700. (j) Wang, Z.-X.; Jia, C.-S.; Zhou, Z.-Y.
Zhou, X.-G. J. Organomet. Chem. 1999, 580, 201.
(2) (a) Coucouvanis, D. Acc. Chem. Res. 1991, 24, 1. (b) Karlin, K.
D. Science 1993, 261, 701. (c) Rao, P. V.; Holm, R. H. Chem. Rev. 2004,
104, 527.
(3) (a) Gloaguen, F.; Lawrence, J. D.; Rauchfuss, T. B. J. Am. Chem.
Soc. 2001, 123, 9476. (b) Gloaguen, F.; Lawrence, J. D.; Schmidt, M.;
Wilson, S. R.; Rauchfuss, T. B. J. Am. Chem. Soc. 2001, 123, 12518.
(c) Lyon, E. J.; Georgakaki, I. P.; Reibenspies, J. H.; Darensbourg, M.
Y. J. Am. Chem. Soc. 2001, 123, 3268. (d) Darensbourg, M. Y.; Lyon,
E. J.; Zhao, X.; Georgakaki, I. P. PNAS 2003, 100, 3683. (e) Song,
L.-C.; Yang, Z.-Y.; Bian, H.-Z.; Hu, Q.-M. Organometallics 2004, 23,
3082.
10.1021/om050333a CCC: $30.25 © 2005 American Chemical Society
Publication on Web 06/17/2005

Starlike Complexes Containing Fe/S Cluster Cores
Organometallics, Vol. 24, No. 15, 2005 3765
the presence of Et3N,4a we made the double-butterfly
one-µ-CO-containing monoanion 2 in 2000 via reaction
of the Grignard reagent RMgX with µ-S2Fe2(CO)6 fol-
lowed by treatment of the intermediate S-centered anion
(µ-S-)(µ-RS)Fe2(CO)6 with Fe3(CO)12.5a In 2002 we
further prepared the two-µ-CO-containing double-but-
terfly dianion 3 by reaction of Fe3(CO)12 with dithiol
HSZSH and Et3N.6a So far, these complex anions 1-3
have been demonstrated to be versatile reagents for
synthesizing a wide variety of Fe/S cluster complexes.4-6
To further develop the chemistry of Fe/S cluster com-
plexes, we recently initiated an investigation on forma-
tion and reactivities of two novel triple-butterfly
three-µ-CO-containing trianions {[(µ-CO)Fe2(CO)6]3-
[(µ-SCH2CH2)3N]}3- (4A) and {[(µ-CO)Fe2(CO)6]3-
[1,3,5-(µ-SCH2)3C6H3]}3- (4B) (Scheme 1), aimed at
obtaining the starlike complexes terminated with three
Fe/S cluster cores. In a previous communication,7 we
preliminarily reported the formation of trianions 4A and
4B, as well as their in situ reactions with some elec-
trophiles leading to five starlike cluster complexes. Now,
in this paper we will report the formation of trianions
4A and 4B in detail and the systematic study concerning
their reactivities toward various electrophiles to produce
15 starlike complexes. In addition, the structural char-
acterization of all the products, including the single-
crystal structures of four representative products, will
also be described.
each of the corresponding intermediates afforded prod-
ucts 5-8 (Scheme 2).
However, when the [Et3NH] salt of trianion 4A was
treated in situ with an electrophile CS2 without a
leaving group, the [Et3NH] salt of an S-centered trianion
was formed via nucleophilic attack of the three nega-
tively charged Fe atoms in 4A at the three C atoms in
three molecules of CS2 followed by loss of the three µ-CO
ligands in 4A. This type of S-centered trianion could be
alkylated in situ with an alkyl halide MeI, PhCH2Br,
or CH2dCHCH2Br to give products 9-11 (Scheme 3).
Products 5-11 are air-stable solids, which were
characterized by elemental analysis and spectroscopy.
For instance, the IR spectra of 5-11 showed three
absorption bands in the region 2085-1972 cm-1 for their
terminal carbonyls, whereas those of 7 and 9-11
displayed one additional absorption band at 1557 cm-1
for the bridged CdN double bonds8,9 or at ca. 1015 cm-1
for the bridged CdS double bonds,10,11 respectively. In
addition, the 31P NMR spectrum of 5 showed one singlet
at 142.45 ppm for its three identical P atoms, which is
very similar to the spectra displayed by single- and
double-butterfly Fe2SP cluster complexes.6b,12 The
1H NMR spectra of the methylene groups attached to
the three bridged S atoms in 5-11 showed one signal
(a triplet or a multiplet) at the chemical shift greater
than 2.2 ppm, which indicates that the methylene
groups are most likely attached to the bridged S atoms
by an equatorial type of bond. This is because the
chemical shifts of the axial and equatorial Me groups
in the a/e isomer of (µ-MeS)2Fe2(CO)6 are 1.62 and
2.13 ppm, respectively.13
Formation and Reactivities of the [Et3NH]
Salt of Trianion {[(µ-CO)Fe2(CO)6]3[1,3,5-(µ-SCH2)3-
C6H3]}3- (4B). Synthesis and Characterization of
Starlike Complexes [(µ-Y)Fe2(CO)6]3[1,3,5-(µ-SCH2)3-
C6H3] (12-19: Y ) Ph2P, PhS, PhCdNPh, CH2d
CHCH2, PhNHCdS, MeSCdS, PhCH2SCdS, CH2d
CHCH2SCdS). The benzene ring-containing trithiol
1,3,5-(HSCH2)3C6H3 could also react with Fe3(CO)12 and
Et3N in 1:3:3 molar ratio in THF at room temperature
to give the [Et3NH] salt of trianion 4B (Scheme 4). The
IR spectrum of 4B in THF, similar to the IR spectra of
anions 1 (R ) Et),4a 3 (Z ) CH2(CH2OCH2)3CH2),6a,b and
4A, showed one medium absorption band at 1738 cm-1
typical of its µ-CO ligands. Further treatment of the
[Et3NH] salt of trianion 4B with electrophiles such as
Ph2PCl, PhSBr, PhC(Cl)dNPh, CH2dCHCH2Br, and
PhNCS or with electrophile CS2 followed by treatment
with organic halides RX, via pathways similar to those
leading to 5-11, gave rise to products 12-19 (Schemes
4 and 5).
Results and Discussion
Formation and Reactivities of the [Et3NH] Salt
of Trianion {[(µ-CO)Fe2(CO)6]3[(µ-SCH2CH2)3N]}3-
(4A). Synthesis and Characterization of Star-
like Complexes [(µ-Y)Fe2(CO)6]3[(µ-SCH2CH2)3N]
(5-11: Y ) Ph2P, PhS, PhCdNPh, CH2dCHCH2,
MeSCdS, PhCH2SCdS, CH2dCHCH2SCdS). Treat-
ment of the nitrogen-containing trithiol N(CH2CH2SH)3
with Fe3(CO)12 and Et3N in 1:3:3 molar ratio in THF at
room temperature resulted in formation of the [Et3NH]
salt of trianion 4A (Scheme 2). The IR spectrum of the
[Et3NH] salt of trianion 4A in THF displayed a medium
absorption band at 1742 cm-1 for its µ-CO ligands,
which is similar to those displayed by the [Et3NH]
salts of the one-µ-CO-containing monoanion 1 (R ) Et)4a
and the two-µ-CO-containing dianion
3
(Z
)
CH2(CH2OCH2)3CH2).6a,b Further in situ treatment of
the [Et3NH] salt of trianion 4A with the electrophiles
containing a leaving group such as Ph2PCl, PhSBr,
PhC(Cl)dNPh, and CH2dCHCH2Br through nucleo-
philic attack of the three negatively charged Fe atoms
in 4A at the S, P, or C atom bearing the leaving group
followed by displacement of the three µ-CO ligands in
The starlike complexes 12-19 are air-stable solids,
which have been characterized by elemental analysis
and spectroscopy. For example, the IR spectra of
(5) For double-butterfly, one-µ-CO-containing monoanion 2, see for
example: (a) Song, L.-C.; Hu, Q.-M.; Fan, H.-T.; Sun, B.-W.; Tang,
M.-Y.; Chen, Y.; Sun, Y. Sun, C.-X.; Wu, Q.-J. Organometallics 2000,
19, 3909. (b) Song, L.-C.; Hu, Q.-M.; Sun, B.-W.; Tang, M.-Y.; Lu
,
G.-L. Inorg. Chim. Acta 2003, 346, 12. (c) Song, L.-C.; Hu, Q.-M.; Sun,
B.-W.; Tang, M.-Y.; Yang, J.; Hua, Y.-J. Organometallics 2002, 21,
1627.
(8) Seyferth, D.; Hoke, J. B. Organometallics 1988, 7, 524.
(9) Song, L.-C.; Lu, G.-L.; Hu, Q.-M.; Qin, X.-D.; Sun, C.-X.; Yang
J.; Sun, J. J. Organomet. Chem. 1998, 571, 55.
(10) Seyferth, D.; Womack, G. B.; Archer, C. M.; Fackler, J. P., Jr.;
Marler, D. O. Organometallics 1989, 8, 443.
(6) For double-butterfly, two-µ-CO-containing dianion 3, see for
example: (a) Song, L.-C.; Fan, H.-T.; Hu, Q.-M. J. Am. Chem. Soc.
2002, 124, 4566. (b) Song, L.-C.; Fan, H.-T.; Hu, Q.-M.; Yang, Z.-Y.;
Sun, Y.; Gong F.-H. Chem. Eur. J. 2003, 9, 170. (c) Song, L.-C.; Gong,
F.-H.; Meng T.; Ge, J.-H.; Cui, L.-N.; Hu, Q.-M. Organometallics 2004,
23, 823.
(11) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Wang R.-J.; Mak, T. C. W.
Organometallics 1995, 14, 5513.
(12) Song, L.-C.; Li, Y.; Hu, Q.-M.; Liu, R.-G.; Wang, J.-T. Acta Chim.
Sin. 1990, 48, 1180.
(13) Seyferth, D.; Henderson, R. S.; Song, L.-C. Organometallics
1982, 1, 125.
(7) Song, L.-C.; Cheng, J.; Hu, Q.-M.; Gong, F.-H.; Bian, H.-Z.; Wang,
L.-X. Organometallics 2005, 24, 472.

3766 Organometallics, Vol. 24, No. 15, 2005
Song et al.
Scheme 2
Scheme 3
displayed by the single- and double-butterfly Fe2PS
cluster complexes.6b,12 It is worth pointing out that the
three methylene groups in 12-19 are probably bound
to the bridged S atoms by equatorial bonds. This is
because in their 1H NMR spectra the methylene groups
showed only one signal (a singlet or a multiplet) at the
chemical shift (>3.5 ppm) which is very close to that
(3.67 ppm) of the equatorial CH2 group in the a/e isomer
of (µ-PhCH2S)2Fe2(CO)6.13 Fortunately, the spectroscopi-
cally characterized structural features for 5-19 men-
tioned above have been unambiguously confirmed by
X-ray crystallographic studies of complexes 5, 12, 15,
and 17 (vide infra).
Crystallographic Studies on 5, 12, 15, and 17. To
confirm the starlike structures of 5-19, X-ray crystal-
lographic studies on 5, 12, 15, and 17 were undertaken.
Their ORTEP drawings are shown in Figures 1-4,
whereas Tables 1-4 list their selected bond lengths and
angles, respectively.
As can be seen in Figures 1 and 2, both 5 and 12
contain three identical Fe2SP butterfly cluster cores in
which each of the P atoms is attached to two phenyl
groups and each of the Fe atoms is attached to three
terminal CO ligands. In addition, the three butterfly
Fe2SP cluster cores in 5 are connected through their S
atoms to three â-C atoms of the central triethyl-
12-19 displayed three absorption bands in the range
2073-1955 cm-1 for their terminal carbonyls. In addi-
tion, while the IR spectrum of 14 showed one additional
absorption band at 1557 cm-1 for its bridged CdN
double bonds,8,9 16-19 displayed one additional band
in the range 1026-1016 cm-1 for their bridged CdS
double bonds.10,11 The 31P NMR spectrum of 12 exhibited
one singlet at 141.31 ppm for its three identical P atoms,
which is almost the same as that displayed by the triple-
butterfly Fe2PS cluster 5 and very close to those

Starlike Complexes Containing Fe/S Cluster Cores
Organometallics, Vol. 24, No. 15, 2005 3767
Scheme 4
respectively. In 15 the C-C bond lengths of the allyl
ligands (for example, C(19)-C(20) ) 1.374 (11) Å and
C(20)-C(21) ) 1.394 (9) Å) lie between the values
reported for the C-C single and CdC double bonds,
indicating that the ligands are best regarded as delo-
calized π-allyl ligands.18 In 17 the bridged CdS double
bonds (for example, the double bond C(28)dS(4) )
1.654(12) Å) is slightly shorter than its neighboring
single bond C(28)-S(5) (1.695(10) Å), but markedly
shorter than the remote single bonds S(5)-C(29) (1.818-
(11) Å) and S(1)-C(25) (1.826(9) Å). In addition, the
three identical cluster cores in 15 and 17 are joined
together by connecting their S atoms with three benzylic
C atoms of the planar trimethylene benzene ring moiety
also via three equatorial bonds (for example, for 15 the
nonbonded angle C(28)-S(1)‚‚‚C(20) ) 161.8° and for
17 the nonbonded angle C(25)-S(1)‚‚‚S(4) ) 168.1°).13,14
In fact, the basic geometry of the cluster cores in 15 is
very similar to that of the single-butterfly cluster
complex (µ-EtS)(µ-CH2dCHCH2)Fe2(CO)6.18 It is worthy
of note that although some double-butterfly Fe2S2C
clusters were recently crystallographically character-
ized,6a,b 17 is the first crystallographically characterized
triple-butterfly Fe2S2C cluster compound.
In summary, we have synthesized and fully charac-
terized the first examples of the starlike complexes with
three terminal butterfly Fe2SP, Fe2S2, Fe2CNS, Fe2C3,
or Fe2S2C cluster cores and a pyramidal N atom or a
planar benzene ring at the central part of the complexes.
The easy availablity of trianions 4A and 4B from
reaction of trithiol N(CH2CH2SH)3 or 1,3,5-(HSCH2)3C6H3
with Fe3(CO)12 and Et3N, as well as their high nucleo-
philicity toward electrophiles, would make them very
useful synthons in the development of transition metal
chemistry.
Experimental Section
General Comments. All reactions were carried out under
an atmosphere of prepurified nitrogen by using standard
Schlenk and vacuum-line techniques. Tetrahydrofuran (THF)
was distilled from Na/benzophenone ketyl under nitrogen.
Fe3(CO)12,19 Ph2PCl,20 N(CH2CH2SH)3,21 1,3,5-(HSCH2)3C6H3,22
PhSBr,23 and PhC(Cl)dNPh24 were prepared according to
literature procedures. Et3N, CS2, MeI, PhCH2Br, CH2dCHCH2-
Br, and PhNCS were of commercial origin and used without
further purification. Preparative TLC was carried out on glass
plates (25 × 15 × 0.25 cm) coated with silica gel G (10-
40 µm). IR spectra were recorded on a Bio-Rad FTS 135
infrared spectrophotometer. 1H(31P) NMR spectra were taken
on a Bruker AC-P200 or Bruker Avance 300 NMR spectrom-
eter. Elemental analyses were performed with an Elementar
Vario EL analyzer. Melting points were determined on a
Yanaco MP-500 apparatus and were uncorrected.
eneamine structural unit by three equatorial bonds (for
example, the nonbonded angle C(2)-S(1)‚‚‚P(1) ) 161.1°),
while those in 12 are bound through their S atoms to
three R-C atoms of the central trimethylenebenzene
moiety by three equatorial bonds (for example, the
nonbonded angle C(19)-S(1)‚‚‚P(1) ) 161.3°). Such
conformational arrangements are necessary to avoid the
strong axial-axial repulsions between the axially bonded
bulky phenyl groups at P atoms and the central part of
the starlike complex.13,14 To our knowledge, 5 and 12
are the first examples of the crystallographically char-
acterized triple-butterfly Fe2PS cluster complexes, al-
though the crystallographically characterized single-
butterfly Fe2PS clusters (µ-PhS)(µ-Ph2P)Fe2(CO)6,15
(µ-t-BuS)(µ-Ph2P)Fe2(CO)6,16 and (µ-t-BuS)(µ-PhClP)
Standard in Situ Preparations of the [Et3NH] Salts of
Trianions {[(µ-CO)Fe2(CO)6]3[(µ-SCH2CH2)3N]}3- (4A) and
{[(µ-CO)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3]}3- (4B). A 100 mL
three-necked flask fitted with a magnetic stir-bar, a rubber
17
Fe2(CO)6 were known.
Figures 3 and 4 show that 15 and 17 have three
identical butterfly Fe2SC3 and Fe2S2C cluster cores,
(18) Seyferth, D.; Womack, G. B.; Dewan, J. C. Organometallics
1985, 4, 398.
(14) Song, L.-C.; Lu, G.-L.; Hu, Q.-M.; Sun, J. Organometallics 1999,
18, 5429.
(19) King, R. B. Organometallic Syntheses; Transition-Metal Com-
pounds; Academic Press: New York, 1965; Vol. 1, p 95.
(20) Horner, L.; Beck, P.; Toscano, V. G. Chem. Ber. 1961, 94, 2122.
(21) Harley-Mason, J. J. Chem. Soc. 1947, 320.
(22) Whitesides, G. M.; Houk, J. J. Am. Chem. Soc. 1987, 109, 6825.
(23) Harpp, D. N.; Mathiaparanam, P. J. Org. Chem. 1972, 37, 1367.
(24) Vaughan, W. R.; Carlson, R. D. J. Am. Chem. Soc. 1962, 84,
769.
(15) Le Borgne, G.; Mathieu, R. J. Organomet. Chem. 1981, 208,
201.
(16) Song, L.-C.; Hu, Q.-M.; Zhou, Z.-Y.; Hu, G.-Z. Chin. J. Org.
Chem. 1991, 11, 533.
(17) Song, L.-C.; Wang, R.-J.; Li, Y.; Wang, H.-G.; Wang, J.-T. Chin.
J. Org. Chem. 1989, 9, 512.

3768 Organometallics, Vol. 24, No. 15, 2005
Song et al.
Scheme 5
Table 1. Selected Bond Lengths (Å) and Angles
(deg) for 5
Table 3. Selected Bond Lengths (Å) and Angles
(deg) for 15
Fe(1)-S(2)
Fe(2)-S(2)
Fe(3)-P(1)
Fe(4)-P(1)
N(1)-C(1)
2.268(3)
2.262(2)
2.227(2)
2.222(2)
1.435(8)
Fe(1)-P(3)
Fe(2)-P(3)
Fe(3)-S(1)
Fe(4)-S(1)
Fe(1)-Fe(2)
2.216(2)
2.225(2)
2.266(2)
2.283(2)
2.5550(19)
Fe(1)-Fe(2)
Fe(3)-Fe(4)
Fe(5)-Fe(6)
Fe(2)-S(1)
Fe(2)-C(21)
Fe(3)-S(2)
2.6778(13)
2.7330(12)
2.6790(14)
2.2402(19)
2.0936(6)
2.243(2)
Fe(1)-C(19)
Fe(4)-S(2)
Fe(5)-S(3)
Fe(6)-S(3)
C(19)-C(20)
Fe(1)-C(1)
2.121(8)
2.2327(17)
2.2391(16)
2.2370(18)
1.374(11)
1.784(8)
S(2)-Fe(1)-Fe(2)
P(3)-Fe(2)-S(2)
P(3)-Fe(2)-Fe(1)
S(1)-Fe(3)-Fe(4)
P(3)-Fe(1)-S(2)
S(2)-Fe(2)-Fe(1)
55.54(7)
P(1)-Fe(3)-S(1)
P(1)-Fe(3)-Fe(4)
P(1)-Fe(4)-S(1)
C(21)-N(1)-C(1)
N(1)-C(1)-C(2)
C(1)-N(1)-C(41)
76.53(8)
54.91(6)
76.29(8)
116.4(7)
117.2(6)
113.4(7)
76.32(8)
54.73(7)
56.21(6)
76.35(8)
55.78(8)
S(1)-Fe(1)-C(19) 86.4(3)
S(1)-Fe(1)-Fe(2) 53.25(5)
C(21)-Fe(2)-S(1) 84.6(2)
S(1)-Fe(2)-Fe(1) 53.45(5)
C(22)-Fe(3)-S(2) 85.13(14) C(19)-C(20)-Fe(1) 59.3(4)
S(2)-Fe(3)-Fe(4) 52.20(5) C(23)-C(22)-Fe(3) 88.94(13)
C(24)-Fe(4)-S(2)
S(2)-Fe(4)-Fe(3)
Fe(2)-S(1)-Fe(1)
Fe(4)-S(2)-Fe(3)
86.02(12)
52.53(5)
73.29(6)
75.27(6)
Table 2. Selected Bond Lengths (Å) and Angles
(deg) for 12
Table 4. Selected Bond Lengths (Å) and Angles
(deg) for 17
Fe(1)-S(1)
Fe(2)-S(1)
P(1)-C(7)
Fe(1)-P(1)
2.264(4)
2.259(3)
1.820(14)
2.226(3)
Fe(1)-Fe(2)
P(1)-C(13)
Fe(2)-P(1)
S(1)-C(19)
2.566(3)
1.817(11)
2.226(4)
1.826(12)
Fe(1)-Fe(2)
Fe(3)-Fe(4)
Fe(5)-Fe(6)
Fe(2)-S(1)
Fe(2)-S(4)
2.618(2)
2.620(2)
2.607(3)
2.253(3)
2.276(3)
Fe(3)-S(2)
Fe(3)-S(6)
S(5)-C(28)
S(4)-C(28)
S(6)-C(30)
2.242(3)
2.280(5)
1.695(10)
1.654(12)
1.655(16)
S(1)-Fe(1)-Fe(2)
P(1)-Fe(2)-S(1)
P(1)-Fe(2)-Fe(1)
C(7)-P(1)-Fe(1)
C(7)-P(1)-Fe(2)
55.34(9)
76.59(13) P(1)-Fe(1)-Fe(2)
54.82(10) S(1)-Fe(2)-Fe(1)
122.0(5)
120.8(5)
P(1)-Fe(1)-S(1)
76.47(13)
54.81(10)
55.55(11)
S(1)-Fe(1)-Fe(2)
S(1)-Fe(2)-S(4)
S(2)-Fe(3)-Fe(4)
S(6)-Fe(3)-Fe(4)
S(2)-Fe(4)-Fe(3)
54.36(8)
S(1)-Fe(2)-Fe(1)
54.80(8)
77.89(10)
84.58(17)
70.83(9)
91.5(3)
C(13)-P(1)-Fe(1) 122.1(4)
Fe(2)-P(1)-Fe(1) 70.37(11)
82.41(12) S(4)-Fe(2)-Fe(1)
54.55(8)
S(2)-Fe(3)-S(6)
76.84(13) Fe(2)-S(1)-Fe(1)
septum, and a nitrogen inlet tube was charged with Fe3(CO)12
(0.75 g, 1.5 mmol), THF (20 mL), Et3N (0.21 mL, 1.5 mmol),
and N(CH2CH2SH)3 (0.065 mL, 0.5 mmol) or 1,3,5-(HSCH2)3-
C6H3 (0.114 g, 0.5 mmol). The mixture was stirred at room
temperature for 0.5-1 h to give a brown-red solution of ca.
0.5 mmol of the intermediate salt 4A‚[Et3NH]3 or 4B‚[Et3NH]3,
which was utilized immediately in the following preparations.
Preparation of [(µ-Ph2P)Fe2(CO)6]3[(µ-SCH2CH2)3N] (5).
To the above prepared solution of 4A‚[Et3NH]3 was added
Ph2PCl (0.36 mL, 2.0 mmol). The mixture was stirred at room
temperature for 24 h. Solvent was removed under reduced
pressure. The residue was subjected to TLC using acetone/
petroleum ether (v/v ) 1:4) as eluent to give 5 (0.255 g,
32%) as a red solid, mp 78-80 °C. Anal. Calcd for C60H42Fe6-
NO18P3S3: C, 45.35; H, 2.66; N, 0.88. Found: C, 45.33; H, 2.67;
54.16(8)
C(28)-S(4)-Fe(2)
S(4)-C(28)-S(5)
Fe(3)-S(2)-C(26) 112.9(3)
123.7(6)
1H NMR (CDCl3): 2.46 (t, J ) 7.0 Hz, 6H, 3SCH2), 2.65
(t, J ) 7.0 Hz, 6H, 3NCH2), 7.19-7.61 (m, 30H, 6C6H5). 31P
NMR (121.48 MHz, CDCl3, 85% H3PO4): 142.45 (s) ppm.
Preparation of [(µ-PhS)Fe2(CO)6]3[(µ-SCH2CH2)3N] (6).
The same procedure was followed as for 5, but PhSBr
(0.567 g, 3.0 mmol) was used instead of Ph2PCl and the residue
was subjected to TLC using CH2Cl2/petroleum ether (v/v ) 1:2)
as eluent. 6 (0.222 g, 33%) was obtained as a red solid, mp
54-56 °C. Anal. Calcd for C42H27Fe6NO18S6: C, 37.06; H, 2.00;
N, 1.03. Found: C, 36.96; H, 2.04; N, 1.02. IR (KBr disk):
νCtO 2073 (s), 2036 (vs), 1995 (vs) cm-1 1H NMR (CDCl3):
.
2.28-2.82 (m, 12H, 3SCH2, 3NCH2), 7.10-7.48 (m, 15H,
3C6H5) ppm.
N, 1.00. IR (KBr disk): νCtO 2059 (s), 2020 (vs), 1982 (vs) cm-1
.

Starlike Complexes Containing Fe/S Cluster Cores
Organometallics, Vol. 24, No. 15, 2005 3769
Figure 1. ORTEP drawing of 5 with atom-labeling
scheme.
Figure 3. ORTEP drawing of 15 with atom-labeling
scheme.
Figure 2. ORTEP drawing of 12 with atom-labeling
scheme.
Figure 4. ORTEP drawing of 17 with atom-labeling
scheme.
Preparation of [(µ-PhCdNPh)Fe2(CO)6]3[(µ-SCH2-
CH2)3N] (7). The same procedure was followed as for 6, but
PhC(Cl)dNPh (0.54 g, 2.5 mmol) was employed in place of
PhSBr. 7 (0.160 g, 20%) was obtained as a red solid, mp 64-
66 °C. Anal. Calcd for C63H42Fe6N4O18S3: C, 48.07; H, 2.69;
N, 3.56. Found: C, 48.23; H, 2.47; N, 3.64. IR (KBr disk):
νCtO 2085 (s), 2030 (s), 1972 (vs); νCdN 1557 (s) cm-1. 1H NMR
(CDCl3): 2.76-2.79 (m, 6H, 3SCH2), 3.04-3.09 (m, 6H,
3NCH2), 6.51-7.24 (m, 30H, 6C6H5) ppm.
Preparation of [(µ-CH2dCHCH2)Fe2(CO)6]3[(µ-SCH2-
CH2)3N] (8). The same procedure was followed as for 6, but
CH2dCHCH2Br (0.27 mL, 3.0 mmol) was utilized. 8 (0.145 g,
25%) was obtained as a red solid, mp 48-51 °C. Anal. Calcd
for C33H27Fe6NO18S3: C, 34.26; H, 2.35; N, 1.21. Found: C,
34.28; H, 2.22; N, 1.20. IR (KBr disk): νCtO 2062 (s), 2024 (vs),
1980 (vs) cm-1. 1H NMR (CDCl3): 0.47 (d, J ) 12.4 Hz, 6H, 6
anti-FeCHH), 1.96 (d, J ) 6.4 Hz, 6H, 6 syn-FeCHH), 2.47-
2.51(m, 6H, 3SCH2), 2.62-2.67 (m, 6H, 3NCH2), 4.69-4.89
(m, 3H, 3CH) ppm.
and then MeI (0.18 mL, 3.0 mmol) was added. The mixture
was stirred at room temperature for 12 h. Solvent was removed
under reduced pressure. The residue was subjected to TLC
separation using acetone/petroleum ether (v/v ) 1:4) as eluent
to give 9 (0.204 g, 31%) as a red solid, mp 41-42 °C. Anal.
Calcd for C30H21Fe6NO18S9: C, 27.54; H, 1.61; N, 1.07. Found:
C, 27.60; H, 1.71; N, 1.08. IR (KBr disk): νCtO 2067 (s), 2027
(vs), 1993 (vs); νCdS 1018 (s) cm-1 1H NMR (CDCl3): 2.53
.
(s, 9H, 3CH3), 2.65-2.72 (m, 6H, 3SCH2), 2.85-3.05 (m, 6H,
3NCH2) ppm.
Preparation of [(µ-PhCH2SCdS)Fe2(CO)6]3[(µ-SCH2-
CH2)3N] (10). The same procedure was followed as for 9, but
PhCH2Br (0.36 mL, 3.0 mmol) and an eluent of acetone/
petroleum ether (v/v ) 1:2) were used. 10 (0.304 g, 40%)
was obtained as a red solid, mp 59-61 °C. Anal. Calcd for
C48H33Fe6NO18S9: C, 37.55; H, 2.17; N, 0.91. Found: C,37.64;
H, 2.11; N, 1.00. IR (KBr disk): νCtO 2067 (s), 2028 (vs), 1993
(vs); νCdS 1016 (s) cm-1. 1H NMR (CDCl3): 2.71 (t, J ) 8.0 Hz,
6H, 3SCH2), 2.95 (t, J ) 8.0 Hz, 6H, 3NCH2), 4.28 (s, 6H,
3CH2), 7.18-7.30 (m, 15H, 3C6H5) ppm.
Preparation of [(µ-MeSCdS)Fe2(CO)6]3[(µ-SCH2CH2)3N]
(9). To the above prepared solution of 4A‚[Et3NH]3 was added
CS2 (0.18 mL, 3.0 mmol). The mixture was stirred for 0.5 h

3770 Organometallics, Vol. 24, No. 15, 2005
Table 5. Crystal Data and Structural Refinements Details for 5, 12, 15, and 17
Song et al.
5
12
15
17
mol formula
C
60H42Fe6NO18P3S3
C
63H39Fe6O18P3S3‚
C
72H48Fe12O36S6
C33H18Fe6O18S9‚
1.5 CH2Cl2
1735.52
293(2)
0.25 CH2Cl2
1347.35
293(2)
mol wt
temp/K
cryst syst
space group
a/Å
1589.14
298(2)
2351.66
293(2)
triclinic
P1h
orthorhombic
Pna2(1)
18.1190 (7)
14.9011(6)
25.4867(10)
90
rhombohedral
R3hc
28.598(5)
28.598(5)
32.224(10)
90
triclinic
P1h
14.9871(19)
16.828(2)
20.682(4)
99.362(3)
104.027(3)
110.708(2)
4552.8(12)
2
13.612(5)
14.753(6)
15.879(6)
64.381(7)
70.868(7)
81.534(8)
2716.4(18)
2
b/Å
c/Å
R/deg
â/deg
90
90
90
120
γ/deg
V/Å3
6881.2(5)
4
22823(9)
12
Z
Dc/g cm-3
abs coeff/mm-1
F(000)
1.534
1.515
1.647
1.458
1.428
2.069
1.991
3208
10 476
1341
limiting indices
-23 e h e 22
-19 e k e 18
-18 e l e 32
ω-2θ
-34 e h e 22
-23 e k e 34
-23 e l e 38
ω-2θ
-17 e h e 17
-18 e k e 20
-22 e l e 24
ω-2θ
-16 e h e 15
-11 e k e 7
-18 e l e 18
ω-2θ
scan type
no. of rflns
no. of indep rflns
2θmax/deg
41 099
31 536
24 902
13 970
11 033
4482
15 881
9525
54.00
50.00
50.06
50.00
R
Rw
0.0468
0.0800
0.0524
0.0811
0.0840
0.1795
0.1060
0.2065
gooodness of fit
largest diff peak
and hole/e Å-3
1.000
0.953
1.017
1.015
0.496/-0.369
0.958/-0.470
0.436/-0.432
1.145/-0.689
Preparation of [(µ-CH2dCHCH2SCdS)Fe2(CO)6]3[(µ-
SCH2CH2)3N] (11). The same procedure was followed as for
9, but CH2dCHCH2Br (0.27 mL, 3.0 mmol) and an eluent of
CH2Cl2/petroleum ether (v/v ) 1:2) were utilized. 11 (0.185 g,
27%) was obtained as a red solid, mp 43-45 °C. Anal. Calcd
for C36H27Fe6NO18S9: C, 31.21; H, 1.96; N, 1.01. Found: C,
31.18; H, 2.00; N, 1.10. IR (KBr disk): νCtO 2067 (s), 2028 (vs),
Preparation of [(µ-CH2dCHCH2)Fe2(CO)6]3[1,3,5-(µ-
SCH2)3C6H3] (15). The same procedure was followed as for
13, except that CH2dCHCH2Br (0.27 mL, 3.0 mmol) was used.
15 (0.224 g, 38%) was obtained as a red solid, mp 64-65 °C.
Anal. Calcd for C36H24Fe6O18S3: C, 36.80; H, 2.06. Found: C,
36.68; H, 2.03. IR (KBr disk): νCtO 2043 (vs), 1989 (vs), 1955
1
(s) cm-1. H NMR (CDCl3): 0.47(d, J ) 12.8 Hz, 6H, 6 anti-
1994 (vs); νCdS 1017 (s) cm-1 1H NMR (CDCl3): 2.69 (br s,
.
FeCHH), 1.96 (d, J ) 6.4 Hz, 6H, 6 syn-FeCHH), 3.58 (s, 6H,
3CH2), 4.72-4.84 (m, 3H, 3CH), 7.08 (s, 3H, C6H3) ppm.
6H, 3SCH2), 2.92-2.96 (m, 6H, 3NCH2), 3.72 (d, J ) 6.5 Hz,
6H, 3CSCH2), 5.18-5.27 (m, 6H, 3CH2d), 5.67-5.76 (m, 3H,
3CH) ppm.
Preparation of [(µ-PhNHCdS)Fe2(CO)6]3[1,3,5-(µ-SCH2)3-
C6H3] (16). The same procedure was followed as for 13, but
PhNCS (0.36 mL, 3.0 mmol) was employed. 16 (0.330 g, 45%)
was obtained as a red solid, mp 110-112 °C. Anal. Calcd for
C48H27Fe6O18N3S6: C, 39.46; H, 1.86; N, 2.29. Found: C, 39.48;
H, 1.88; N, 2.27. IR (KBr disk): νCtO 2066 (s), 2026 (vs), 1988
(vs); νCdS 1026 (m) cm-1. 1H NMR (CDCl3): 3.74-3.94 (m, 6H,
3CH2), 7.26-7.46 (m, 18H, C6H3, 3C6H5), 8.67 (s, 3H, 3NH)
ppm.
Preparation of [(µ-MeSCdS)Fe2(CO)6]3[1,3,5-(µ-SCH2)3-
C6H3] (17). The above prepared solution of 4B‚[Et3NH]3 was
cooled to -40 °C. To this cooled solution was added CS2
(0.18 mL, 3.0 mmol). The mixture was stirred at this temper-
ature for 1 h, and then MeI (0.19 mL, 3.0 mmol) was added.
The mixture was warmed to room temperature and then was
stirred for 24 h. Solvent was removed under reduced pressure.
The residue was subjected to TLC separation using CH2Cl2/
petroleum ether (v/v ) 1:2) as eluent to give 17 (0.297 g, 45%)
as a red solid, mp 56-58 °C. Anal. Calcd for C33H18Fe6O18S9:
C, 29.89; H, 1.37. Found: C, 30.07; H, 1.40. IR (KBr disk):
νCtO 2066 (s), 2028 (vs), 1993 (vs); νCdS 1017 (s) cm-1. 1H NMR
(CDCl3): 2.53 (s, 9H, 3CH3), 3.77(s, 6H, 3CH2), 7.20-7.40
(m, 3H, C6H3) ppm.
Preparation of [(µ-Ph2P)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3]
(12). The above prepared solution of 4B‚[Et3NH]3 was cooled
to -40 °C. To this cooled solution was added Ph2PCl (0.26 mL,
1.5 mmol). The mixture was warmed to room temperature and
then was stirred for 24 h. Solvent was removed under reduced
pressure. The residue was subjected to TLC separation using
CH2Cl2/petroleum ether (v/v ) 1:2) as eluent to give 12
(0.353 g, 44%) as a red solid, mp 106-108 °C. Anal. Calcd for
C63H39Fe6O18P3S3: C, 47.05; H, 2.44. Found: C, 47.26; H, 2.48.
IR (KBr disk): νCtO 2059 (s), 2020 (vs), 1983 (vs) cm-1. 1H NMR
(CDCl3): 3.84 (s, 6H, 3CH2), 6.52-7.51 (m, 33H, C6H3, 6C6H5).
31P NMR (121.48 MHz, CDCl3, 85% H3PO4): 141.31 (s) ppm.
Preparation of [(µ-PhS)Fe2(CO)6]3[1,3,5-(µ-SCH2)3C6H3]
(13). To the above prepared solution of 4B‚[Et3NH]3 was added
PhSBr (0.567 g, 3.0 mmol). The mixture was stirred at room
temperature for 24 h. After the same workup as for 12, product
13 (0.330 g, 48%) was obtained as a red solid, mp 87-89 °C.
Anal. Calcd for C45H24Fe6O18S9: C, 39.16; H, 1.75. Found: C,
38.99; H, 1.95. IR (KBr disk): νCtO 2073 (s), 2036 (vs), 1997
(vs) cm-1. 1H NMR (CDCl3): 3.51-3.62 (m, 6H, 3CH2), 6.92-
7.42 (m, 18H, C6H3, 3C6H5) ppm.
Preparation of [(µ-PhCdNPh)Fe2(CO)6]3[1,3,5-(µ-SCH2)3-
C6H3] (14). The same procedure was followed as for 13, except
that PhC(Cl)dNPh (0.641 g, 3.0 mmol) was used in place of
PhSBr. 14 (0.338 g, 42%) was obtained as a red solid, mp
142-143 °C. Anal. Calcd for C66H39Fe6O18N3S3: C, 49.75; H,
2.47, N, 2.64. Found: C, 49.68; H, 2.46; N, 2.50. IR (KBr
Preparation of [(µ-PhCH2SCdS)Fe2(CO)6]3[1,3,5-(µ-
SCH2)3C6H3] (18). The same procedure was followed as for
17, but PhCH2Br (0.36 mL, 3.0 mmol) was used instead of MeI
to give 18 (0.271 g, 35%) as a red solid, mp 60-62 °C. Anal.
Calcd for C51H30Fe6O18S9: C, 39.41; H, 1.95. Found: C, 39.68;
H, 1.70. IR (KBr disk): νCtO 2066 (s), 2028 (vs), 1993 (vs);
νCdS 1016 (s) cm-1. 1H NMR (CDCl3): 3.78 (s, 6H, 3SCH2), 4.26
(s, 6H, 3CH2Ph), 7.12-7.45 (m, 18H, C6H3, 3C6H5 ) ppm.
disk): νCtO 2066 (s), 2027 (vs), 1987 (vs), νCdN 1557 (m) cm-1
.
1H NMR (CDCl3): 3.64 (s, 6H, 3CH2), 6.48-7.51 (m, 33H, C6H3,
6C6H5) ppm.

Starlike Complexes Containing Fe/S Cluster Cores
Organometallics, Vol. 24, No. 15, 2005 3771
Preparation of [(µ-CH2dCHCH2SCdS)Fe2(CO)6]3[1,3,5-
(µ-SCH2)3C6H3] (19). The same procedure was followed as for
17, except that CH2dCHCH2Br (0.27 mL, 3.0 mmol) was used
instead of MeI. 19 (0.350 g, 50%) was obtained as a red solid,
mp 65-67 °C. Anal. Calcd for C39H24Fe6O18S9: C, 33.36; H,
1.72. Found: C, 33.72; H, 1.75. IR (KBr disk): νCtO 2067 (s),
thermal parameters for non-hydrogen atoms. The calculations
were performed using the SHELXTL-97 program. Details of
the crystal data, data collections, and structure refinements
are summarized in Table 5.
Acknowledgment. We are grateful to the National
Natural Science Foundation of China, the State Key
Laboratory of Organometallic Chemistry, and the Spe-
cialized Research Fund for the Doctoral Program of
Higher Education of China for financial support of this
work.
2029 (vs), 1994 (vs); νCdS 1016 (s) cm-1 1H NMR (CDCl3):
.
3.70-3.76 (m, 12H, 6SCH2), 5.16-5.26 (m, 6H, 3CH2d), 5.60-
5.80 (m, 3H, 3CHd), 7.34 (s, 3H, C6H3) ppm.
X-ray Structure Determinations of 5, 12, 15, and 17.
While single crystals of 12, 15, and 17 suitable for X-ray
diffraction analysis were grown by slow evaporation of their
CH2Cl2/hexane solutions at 4 °C, the X-ray quality crystals of
5 were produced by slow evaporation of its Et3N/MeOH
solution at 4 °C. Each crystal was mounted on a Bruker
SMART 1000 automated diffractometer with a graphite mono-
chromator with Mo KR radiation (λ ) 0.71073 Å). The
structures were solved by direct methods and expanded by
Fourier techniques. The final refinements were accomplished
by the full-matrix least-squares method with anisotropic
Supporting Information Available: Full tables of crystal
data, atomic coordinates and thermal parameters, and bond
lengths and angles for 5, 12, 15, and 17 as CIF files. This
material is available free of charge via the Internet at
http://pubs. acs.org.
OM050333A