Synthesis and characterization of μ4-S-containing double- and triple-butterfly iron carbonyl complexes. Crystal structures of (μ-EtS)[μ-PhC(O)S][Fe2(CO)6]3(μ 4-S)2 and (μ-t-BuS)2

Article abstract of DOI:10.1016/S0020-1693(02)01382-8

The [MgBr]⁺ salts of the μ₄-S-containing double-butterfly anions {(μ-RS)(μ-CO)[Fe₂(CO)₆]₂(μ ₄-S)}^- (1, R=Ph, p-MeC₆H₄) react in situ with CS₂ fol

Full text of DOI:10.1016/S0020-1693(02)01382-8

Inorganica Chimica Acta 346 (2003) 12ꢃ18
/
www.elsevier.com/locate/ica
Synthesis and characterization of m4-S-containing double- and triple-
butterfly iron carbonyl complexes.
Crystal structures of (m-EtS)[m-PhC(O)S][Fe2(CO)6]3(m4-S)2 and
(m-t-BuS)2[Fe2(CO)6]3(m4-S)2
Li-Cheng Song a,*, Qing-Mei Hu a, Bao-Wei Sun a, Ming-Yi Tang a, Guo-Liang Lu a,b
a Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
b State Key Laboratory of Organometallic Chemistry, Shanghai 200032, China
Received 6 May 2002; accepted 11 October 2002
Abstract
The [MgBr]ꢀ salts of the m4-S-containing double-butterfly anions {(m-RS)(m-CO)[Fe2(CO)6]2(m4-S)}ꢁ (1, Rꢂ
react in situ with CS2 followed by treatment of the corresponding intermediate [MgBr]ꢀ salts of anions {(m-RS)(m-SÄ
CS)[Fe2(CO)6]2(m4-S)}ꢁ (m1) with ClCH2CO2Et to give m4-S-containing double-butterfly iron carbonyl complexes (m-RS)(m-
EtO2CCH2SCÄS)[Fe2(CO)6]2(m4-S) (2a, RꢂPh; 2b, Rꢂ I, Br) salts of
p-MeC6H4), whereas the in situ reaction of the [MgX]ꢀ (Xꢂ
anions 1 (RꢂMe, Et) with m-S2Fe2(CO)6 followed by treatment of the corresponding intermediate salts of anions {(m-RS)(m-
S)[Fe2(CO)6]3(m4-S)2}ꢁ (m2) with PhC(O)Cl produces m4-S-containing unsymmetrical triple-butterfly iron carbonyl complexes (m-
RS)[m-PhC(O)S][Fe2(CO)6]3(m4-S)2 (3a, RꢂMe; 3b, RꢂEt). More interestingly, the symmetrical m4-S-containing triple-butterfly
EtS; 5b, REꢂ p-MeC6H4Se) can be synthesized by
/Ph, p-MeC6H4)
/
/
/
/
/
/
/
/
complexes (m-RE)2[Fe2(CO)6]3(m4-S)2 (5a, REꢂ
/
/
t-BuS; 5c, REꢂ
/
PhSe; 5d, REꢂ
/
reaction of an excess of the [Et3NH]ꢀ salts of the m-CO-containing single-butterfly anions [(m-RE)(m-CO)Fe2(CO)6]ꢁ (4) with m-
S2Fe2(CO)6 and subsequent treatment of the resulting mixture with SO2Cl2. While the function of an excessive 4 for production of
5aꢃ
/
d is proposed, products 2a,b, 3a,b and 5aꢃ
d have been characterized by elemental analysis, and IR and 1H NMR spectroscopy,
as well as for 3b and 5b by X-ray diffraction techniques.
/
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: m-CO butterfly anions; m4-S butterfly complexes; Reactions; Synthesis; Crystal structures
1. Introduction
complexes, we have been interested in studying m4-S-
forming reactions and the reactions involving m4-S-
containing reactive intermediates, which has so far led
us to obtain a variety of double-, triple- and even
It is known that very few m4-S-containing butterfly
iron carbonyl complexes of the type [(m-
RS)Fe2(CO)6]2(m4-S) had been prepared [1ꢃ4] before
1988, when we reported a general and convenient
/
multiple-butterfly iron carbonyl complexes [6ꢃ
paper will describe the synthesis of double- and triple-
butterfly complexes S)
(m-RS)(m-EtO2CCH2SCÄ
[Fe2(CO)6]2(m4-S) (2a, RꢂPh; 2b, Rꢂp-MeC6H4), (m-
RS)[m-PhC(O)S][Fe2(CO)6]3(m4-S)2 (3a, RꢂMe; 3b,
RꢂEt) and (m-RE)2[Fe2(CO)6]3(m4-S)2 (5a, REꢂEtS;
5b, REꢂt-BuS; 5c, REꢂPhSe; 5d, REꢂp-
/10]. This
procedure for synthesis of such m4-S-containing dou-
/
/
/
ble-butterfly complexes [(m-RS)Fe2(CO)6]2(m4-S) (Rꢂ
Me, Et, PhCH2, p-MeC6H4, PhCÅC) in high yield
(61ꢃ91%) [5]. In view of the novelty and diversity of
/
/
/
/
/
/
/
/
/
structures and reactivities concerning m4-S iron carbonyl
MeC6H4Se), and the structural characterization of these
new m4-S-containing complexes by elemental analysis,
spectroscopy, and particularly for 3b and 5b by X-ray
diffraction analysis.
* Corresponding author.
E-mail address: lcsong@public.tpt.tj.cn (L.-C. Song).
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01382-8

L.-C. Song et al. / Inorganica Chimica Acta 346 (2003) 12ꢃ
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13
2. Results and discussion
order to avoid the sterically strong repulsions between
these groups and the structural moieties axially bonded
to their neighboring bridged S atoms [6,7]. Fortunately,
this has been confirmed by crystal X-ray diffraction
analysis of 3b. The molecular structure of 3b is shown in
Fig. 1, whereas its selected bond lengths and angles are
given in Table 1. Fig. 1 shows that 3b contains three
butterfly cores Fe(3)Fe(4)S(1)S(3), Fe(1)Fe(2)S(1)S(2)
and Fe(5)Fe(6)S(2)S(4) joined together by two m4-S
atoms of S(1) and S(2). While each of the Fe atoms
from Fe(1) to Fe(6) is bound to three terminal carbo-
nyls, the PhCO and Et groups are indeed bonded to the
bridged S atoms of S(3) and S(4) by an equatorial type
of bond, respectively. It is worthy of note that in the
three butterfly cores the geometric parameters of the
middle butterfly core are somewhat different from those
2.1. Synthesis and characterization of (m-RS)(m-
EtO2CCH2SCÄ
/
S)[Fe2(CO)6]2(m4-S) (2a,b)
Interestingly, we have found that the m-CO-contain-
ing double-butterfly anions {(m-RS)(m-CO)[Fe2-
(CO)6]2(m4-S)}ꢁ (1, Rꢂ
/
Ph, p-MeC6H4) (prepared as
their [MgBr]ꢀ salts from a sequential reaction of m-
S2Fe2(CO)6, Grignard reagents RMgBr and Fe3(CO)12)
reacted in situ with CS2 followed by treatment of the
corresponding intermediate [MgBr]ꢀ salts of anions
{(m-RS)(m-SÄ
CS)[Fe2(CO)6]2(m4-S)}ꢁ (m1) [9] with
/
ClCH2CO2Et to afford the S-functionalized double-
butterfly iron carbonyl complexes 2a,b (Scheme 1).
Complexes 2a,b are new and were characterized by
elemental analysis and spectroscopy. For example, while
of the two side butterfly cores. For example, the bond
˚
length of Fe(3)Ã
/
Fe(4) (2.5156(11) A) or Fe(5)Ã
/
Fe(6)
1
the H NMR spectra of 2a,b displayed the correspond-
˚
(2.5166(13) A) is shorter than that of Fe(1)Ã
/Fe(2)
ing resonance signals for their R and CH2CO2Et groups,
the IR spectra showed one absorption band at 1739 and
1740 cmꢁ1 for their ester carbonyls and one absorption
˚
(2.5699(12) A), and the dihedral angle between Fe(3)Ã
Fe(4)ÃS(1) and Fe(3)ÃFe(4)ÃS(3) (84.548) or Fe(5)Ã
Fe(6)ÃS(2) and Fe(5)ÃFe(6)ÃS(4) (83.778) is larger
than that between Fe(1)ÃFe(2)ÃS(1) and Fe(1)ÃFe(2)Ã
S(2) (72.598).
/
/
/
/
/
/
/
/
band at 1020 and 1010 cmꢁ1 for their coordinated CÄ
/S
/
/
/
/
double bonds [11].
2.2. Synthesis and characterization of (m-RS)[m-
PhC(O)S][Fe2(CO)6]3(m4-S)2 (3a,b). Crystal
structure of 3b
2.3. Synthesis and characterization of (m-
RE)2[Fe2(CO)6]3(m4-S)2 (5aꢃd). Crystal structure of
5b
/
We have further found that the [MgX]ꢀ (Xꢂ
salts of anions (1, Rꢂ
S2Fe2(CO)6 followed by treatment of the corresponding
intermediate [MgX]ꢀ salts of anions {(m-RS)(m-
S)[Fe2(CO)6]3(m4-S)2}ꢁ (m2) [9] with PhC(O)Cl to give
the S-functionalized triple-butterfly iron carbonyl com-
plexes 3a,b (Scheme 2).
/
Br, I)
More interestingly, the [Et3NH]ꢀ salts of the m-CO-
containing single-butterfly anions [(m-RE)(m-CO)-
Fe2(CO)6]ꢁ (4, REꢂ
EtS, t-BuS, PhSe, p-MeC6H4Se)
(prepared from corresponding REH, Fe3(CO)12 and
Et3N) [6,12] could react in situ with approximately 0.5
equiv. (or more less amount) of m-S2Fe2(CO)6 at room
temperature followed by treatment with 0.5 equiv. (or
/
Me, Et) reacted in situ with m-
/
Products 3a,b are also new and were characterized by
elemental analysis, spectroscopy and crystal X-ray
diffraction analysis. For example, the IR spectra of
3a,b showed one absorption band at 1687 and 1684
cmꢁ1 for their carbonyls in benzoyl groups, whereas the
1H NMR spectra of 3a,b exhibited one signal or one set
of signals for their Me, Et and Ph groups. In principle,
the R and PhC(O) groups in 3a,b should be attached to
the bridged S atoms by an equatorial type of bond, in
more less amount) of SO2Cl2 from ꢁ
temperature [8] to give symmetrically R-substituted
triple-butterfly iron carbonyl complexes 5aꢃd (Scheme
3).
In fact, this type of novel tandem reaction leading to
complexes (m-RE)2[Fe2(CO)6]3(m4-S)2 (5b, REꢂt-BuS;
5d, REꢂp-MeC6H4Se) was briefly described in our
communication [8]. In this paper, we wish to report the
experimental details and give more detailed discussion
concerning the synthesis and structural characterization
/
78 8C to room
/
/
/
of 5aꢃ
Complexes 5aꢃ
tal analysis and spectroscopy. For instance, while the IR
spectra of 5aꢃd showed several absorption bands in the
range 2088ꢃ
1922 cmꢁ1 for their terminal carbonyls,
/d all obtained from this type of reaction.
/d have been characterized by elemen-
/
/
1
their H NMR spectra displayed resonance signals for
their respective R groups. In addition, it is worth
pointing out that the two R groups in 5aꢃd, similar to
/
R and PhC(O) groups in 3a,b, should be attached to the
bridged S and/or Se atoms by an equatorial type of
Scheme 1.

14
L.-C. Song et al. / Inorganica Chimica Acta 346 (2003) 12ꢃ18
/
Scheme 2.
bond. This is consistent with the 1H NMR spectra of Et,
t-Bu, Ph and p-MeC6H4 in 5aꢃd showing one signal or
one set of signals, and this has been further confirmed
Table 1
˚
Selected bond lengths (A) and angles (8) for 3b
/
Bond lengths
by the X-ray diffraction analysis of 5b.
Fe(1)Ã
Fe(1)Ã
Fe(2)Ã
Fe(3)Ã
Fe(4)Ã
Fe(5)Ã
Fe(6)Ã
/
Fe(2)
S(1)
S(1)
S(1)
S(1)
S(4)
S(4)
2.5699(12) Fe(1)Ã
2.2668(16) Fe(2)Ã
2.2639(15) Fe(3)Ã
2.2725(16) Fe(3)Ã
2.2835(15) Fe(5)Ã
/
S(2)
S(2)
S(3)
Fe(4)
S(2)
Fe(6)
S(2)
2.2560(16)
2.2623(16)
2.2619(17)
2.5156(11)
2.2654(15)
2.5166(13)
2.2772(17)
/
/
Fig. 2 shows the molecular structure of 5b and Table 2
lists its selected bond lengths and angles. As seen in Fig.
2, 5b comprises the three butterfly-shaped Fe2S2 sub-
cluster cores Fe(1)Fe(2)S(1)S(2), Fe(3)Fe(3a)S(2)S(2a),
and Fe(1a)Fe(2a)S(1a)S(2a). In addition, each Fe atom
has three terminal CO ligands, and the two t-Bu groups
are indeed bonded to S(1) and S(1a) atoms by an
equatorial bond. This molecule is chiral, which has a C2
/
/
/
/
/
/
/
2.2700(19) Fe(5)Ã
/
/
2.262(2)
Fe(6)Ã
/
Bond angles
S(2)ÃFe(1)Ã
S(2)ÃFe(5)Ã
S(2)ÃFe(2)Ã
S(3)ÃFe(3)Ã
S(4)ÃFe(6)Ã
Fe(2)ÃS(1)Ã
Fe(1)ÃS(2)Ã
/
/
S(1)
83.15(6)
56.58(5)
83.07(6)
76.48(6)
56.43(5)
128.42(7)
69.33(5)
S(2)Ã
S(2)Ã
S(1)Ã
S(1)Ã
Fe(2)Ã
Fe(1)Ã
Fe(1)Ã
/
Fe(5)Ã
Fe(1)Ã
Fe(2)Ã
Fe(3)Ã
S(1)Ã
S(1)Ã
S(2)Ã
/
S(4)
76.59(6)
55.45(5)
55.50(4)
56.69(4)
69.11(5)
129.83(7)
141.11(7)
/
/
Fe(6)
S(1)
S(1)
/
/
Fe(2)
Fe(1)
Fe(4)
Fe(1)
Fe(3)
Fe(5)
/
/
/
/
axis passing through the two midpoints of Fe(3)Ã
/
Fe(3a)
/
/
/
/
and S(2)Á Á ÁS(2a). It is noteworthy that the geometric
parameters of the middle subcluster core are somewhat
different from those of the two identical side subcluster
/
/
Fe(5)
Fe(3)
Fe(2)
/
/
/
/
/
/
/
/
/
/
cores. For example, the dihedral angle between Fe(3)Ã
Fe(3a)ÃS(2) and Fe(3)ÃFe(3a)ÃS(2a) (73.78) is less than
that between Fe(1)ÃFe(2)ÃS(1) and Fe(1)ÃFe(2)ÃS(2)
or Fe(1a)ÃFe(2a)ÃS(1a) and Fe(1a)ÃFe(2a)ÃS(2a)
(86.18), and the bond length of Fe(3)ÃFe(3a) (2.563(2)
Fe(2) or Fe(1a)ÃFe(2a)
/
/
/
/
˚
/
/
/
/
(2.504(1) A). In fact, this triple-butterfly cluster is very
similar to cluster 3b described above.
/
/
/
/
/
Finally, it should be noted that although the reaction
˚
A) is longer than that of Fe(1)Ã
/
/
mechanism for the formation of 5aꢃd is not completely
/
Fig. 1.

L.-C. Song et al. / Inorganica Chimica Acta 346 (2003) 12ꢃ
/18
15
Table 2
˚
Selected bond lengths (A) and angles (8) for 5b
Bond lengths
Fe(1)Ã
Fe(1)Ã
Fe(2)Ã
Fe(3)Ã
/
Fe(2)
2.504(1) Fe(1)Ã
2.275(2) Fe(2)Ã
2.270(2) Fe(3)Ã
2.256(1) Fe(3)Ã
2.256(1) S(1)Ã
/
S(2)
2.277(2)
2.260(2)
2.253(2)
2.563(2)
/S(1)
/S(1)
/S(2)
/S(2)
/S(2a)
/Fe(3a)
Scheme 3.
Fe(3a)Ã
Bond angles
Fe(2)ÃS(2)Ã
S(2)ÃFe(1)Ã
S(1)ÃFe(2)Ã
S(2)ÃFe(3)Ã
S(2)ÃFe(3)Ã
Fe(1)ÃS(2)Ã
/S(2)
/
C(11)
1.879(11)
understood as yet, we might propose a possible path-
way, on the basis of the well-known properties of both
anions [(m-RS)(m-S)Fe2(CO)6]ꢁ and [(m-RE)(m-CO)-
Fe2(CO)6]ꢁ (4) [6,13], to account for the production
/
/
Fe(3)
S(1)
S(2)
130.3(1) Fe(2)Ã
74.9(1) Fe(1)Ã
75.3(1) S(2)ÃFe(1)Ã
55.4(1) S(1)ÃFe(2)Ã
82.3(1) Fe(3a)Ã
66.8(1) Fe(1)ÃS(2)Ã
/
S(1)Ã
Fe(2)Ã
/
Fe(1)
67.0(1)
56.7(1)
56.5(1)
56.8(1)
55.3(1)
139.8(1)
/
/
/
/S(2)
/
/
/
/Fe(2)
/
/
Fe(3a)
S(2a)
Fe(2)
/
/Fe(1)
/
/
/
Fe(3)Ã
/S(2a)
of 5aꢃd.
/
/
/
/
/Fe(3)
This pathway, as shown in Scheme 4, actually
includes three major steps: (i) the negatively charged
Fe atom of anions 4 attacks the S atom of m-S2Fe2(CO)6,
followed by loss of the m-CO ligand from intermediates
m3 to give the S-centered intermediate anions m4; (ii) the
attack of the negatively charged S atom of m4 at the S
atom of SO2Cl2 gives rise to intermediates m5; (iii) the
bridged S atom attached to the SO2Cl group in m5 is
attacked by the negatively charged Fe atom of the excess
amount of anions 4, followed by loss of the SO2Cl group
tilled from Na/benzophenone ketyl under nitrogen.
Fe3(CO)12 [14], m-S2Fe2(CO)6 [15] and Grignard re-
agents RMgX [16] were prepared according to literature
procedures, whereas the others used in this paper were
of commercial origin and used without further purifica-
tion. Preparative TLC was carried out on glass plates
(26ꢄ
/
20ꢄ
/
0.25 cm) coated with silica gel H (10ꢃ40 mm).
/
IR spectra were recorded on a Bruker Vector 22 infrared
1
spectrophotometer. H NMR spectra were recorded on
and m-CO ligand to produce 5aꢃ
proved that when the ratio of the starting materials
(anions 4: m-S2Fe2(CO)6ꢃSO2Cl2 is approximately 1:1:1
or less anions 4) is used in this type of reaction, products
5aꢃd cannot be obtained. This has not only indicated
the function of an excess of anions 4 played in the
formation of 5aꢃd, but also gives an additional evidence
/
d. Up to now, we have
a Bruker AC-P200 NMR spectrometer. C/H analyses
were performed on an Elementar Vario EL analyzer.
M.p.s were determined on a Yanaco MP-500 apparatus
and were uncorrected.
/
/
/
for the suggested pathway described above.
3.1. Preparation of (m-PhS)(m-EtO2CCH2SCÄ
/
S)[Fe2(CO)6]2(m-S) (2a)
3. Experimental
A 100 ml two-necked flask equipped with a stir-bar, a
N2 inlet tube, and a serum cap was charged with 0.172 g
(0.5 mmol) of m-S2Fe2(CO)6 and 20 ml of THF. The
All reactions were carried out under an atmosphere of
prepurified nitrogen using standard Schlenk and va-
cuum-line techniques. Tetrahydrofuran (THF) was dis-
resulting red solution was stirred and cooled to ꢁ
/
78 8C
using a dry ice/C3H6O bath. To this solution was
Fig. 2.

16
L.-C. Song et al. / Inorganica Chimica Acta 346 (2003) 12ꢃ18
/
Scheme 4.
injected a given amount of Grignard reagent PhMgBr in
Et2O by a syringe until the solution turned to emerald
green. To this solution was added 0.252 g (0.5 mmol) of
Fe3(CO)12 and then the mixture was warmed to room
temperature (r.t.). The mixture was stirred at this
temperature for 1 h to give a solution of the [MgBr]ꢀ
salt of anion {(m-PhS)(m-CO)[Fe2(CO)6]2(m4-S)}ꢁ. To
this solution was added 0.10 ml (1.8 mmol) of CS2 and
CH3), 2.28 (s, 3H, ArCH3), 4.05ꢃ
/
4.40 (m, 4H, 2CH2),
7.07ꢃ7.50 (m, 4H, C6H4).
/
3.3. Preparation of (m-MeS)[m-
PhC(O)S][Fe2(CO)6]3 (m4-S)2 (3a)
To the [MgI]ꢀ salt of anion {(m-MeS)(m-CO)[Fe2-
(CO)6]2(m4-S)}ꢁ prepared from MeMgI, m-S2Fe2(CO)6
and Fe3(CO)12 was added 0.172 g (0.5 mmol) of m-
S2Fe2(CO)6. The mixture was stirred for 2 h at r.t. and
then 0.16 ml (1.3 mmol) of PhC(O)Cl was added. The
new mixture was stirred at this temperature for 10 h.
Solvent was removed under reduced pressure and the
residue was subjected to TLC separation using petro-
leum ether as eluent. From the main red band 0.161 g
the mixture was stirred at r.t. for 1 h to give a redꢃ
/
brown solution. To this solution was added 0.1 ml (0.9
mmol) of ClCH2CO2Et and the mixture was stirred at
this temperature for 12 h. Solvent was removed under
reduced pressure and the residue was subjected to TLC
separation using CH2Cl2/petroleum ether (v/vꢂ
eluent. From the main orangeꢃred band 0.200 g (46%)
of 2a was obtained as a red solid. M.p. 35ꢃ36 8C. Anal.
/2:5) as
/
/
(30%) of 3a was obtained as a brownꢃred solid. M.p.
/
Found: C, 31.98; H, 1.61. Calc. for C23H12Fe4O14S4: C,
31.97; H, 1.40%. IR (KBr disk, cmꢁ1): n(CÅO) 2083(s),
143 8C (dec.). Anal. Found: C, 28.52; H, 0.92. Calc. for
C26H8Fe6O19S4: C, 28.71; H, 0.74%. IR (KBr disk,
cmꢁ1): n(CÅO) 2060(s), 2043(vs), 2007(s); n(CÄO) 1687(m).
2059(vs), 2036(vs), 1997(vs); n(CÄO) 1739(s); n(CÄS)
1
1020(s). H NMR (C3H6O-d6, d, ppm): 1.23 (t, Jꢂ
/
7.6
7.59 (m,
1H NMR (C3H6O-d6, d, ppm): 2.36 (s, 3H, CH3), 7.34ꢃ
/
Hz, 3H, CH3), 4.05ꢃ
/
4.39 (m, 4H, 2CH2), 7.20ꢃ
/
8.20 (m, 5H, C6H5).
5H, C6H5).
3.4. Preparation of (m-EtS)[m-
PhC(O)S][Fe2(CO)6]3(m4-S)2 (3b)
3.2. Preparation of (m-p-MeC6H4S)(m-EtO2CCH2SCÄ
/
S)[Fe2(CO)6]2(m4-S) (2b)
The same procedure as that for 3a was followed, but
the [MgBr]ꢀ salt of anion (m-EtS)(m-CO)[Fe2(CO)6]2(m4-
S)ꢁ prepared from EtMgBr, m-S2Fe2(CO)6 and
Fe3(CO)12 was used instead of the [MgI]ꢀ salt of anion
(m-MeS)(m-CO)[Fe2(CO)6]2(m4-S)ꢁ. From the main red
band 0.082 g (15%) of 3b was obtained as a black solid.
M.p. 144 8C (dec.). Anal. Found: C, 29.26; H, 1.22.
Calc. for C27H10Fe6O19S4: C, 29.44; H, 0.92%. IR (KBr
The same procedure as that for 2a was followed, but
the [MgBr]ꢀ salt of anion {(m-p-MeC6H4S)(m-CO)[Fe2-
(CO)6]2(m4-S)}ꢁ prepared from p-MeC6H4MgBr, m-
S2Fe2(CO)6 and Fe3(CO)12 was used instead of the
[MgBr]ꢀ salt of anion {(m-PhS)(m-CO)[Fe2(CO)6]2(m4-
S)}ꢁ. From the main orangeꢃ
/red band 0.178 g (41%) of
2b was obtained as a red solid. M.p. 61ꢃ63 8C. Anal.
/
Found: C, 33.10; H, 1.61. Calc. for C24H14Fe4O14S4: C,
32.83; H, 1.61%. IR (KBr disk, cmꢁ1): n(CÅO) 2090(s),
2065(vs), 2042(vs), 1993(vs); n(CÄO)) 1740(s); n(CÄS)
disk, cmꢁ1): n(CÅO) 2058(s), 2044(vs), 1993(s); n(CÄO)
1
1684(m). H NMR (C3H6O-d6, d, ppm): 1.43 (t, Jꢂ
/7.4
Hz, 3H, CH3), 2.64 (q, Jꢂ
/
7.4 Hz, 2H, CH2), 7.57ꢃ
/8.16
1
1010(s). H NMR (C3H6O-d6, d, ppm): 1.24 (br.s, 3H,
(m, 5H, C6H5).

L.-C. Song et al. / Inorganica Chimica Acta 346 (2003) 12ꢃ
/18
17
3.5. Preparation of (m-EtS)2[Fe2(CO)6]3(m4-S)2 (5a)
3.8. Preparation of (m-p-MeC6H4Se)2[Fe2(CO)6]3(m4-
S)2 (5d)
A 100 ml two-necked flask with a stir-bar, a N2 inlet
tube, and a serum cap was charged with 0.504 g (1.0
mmol) of Fe3(CO)12, 10 ml of THF, 0.08 ml (1.1 mmol)
of EtSH and 0.17 ml (1.2 mmol) of Et3N. The mixture
The same procedure as that for 5a was followed, but
approximately 1.5 mmol of the [Et3NH]ꢀ salt of anion
[(m-p-MeC6H4Se)(m-CO)[Fe2(CO)6]ꢁ [prepared from
0.765 g (1.5 mmol) of Fe3(CO)12, 0.256 g (1.5 mmol)
of p-MeC6H4SeH and 0.23 ml (1.6 mmol) of Et3N] was
employed in place of approximately 1.0 mmol of the
[Et3NH]ꢀ salt of anion [(m-EtS)(m-CO)Fe2(CO)6]ꢁ.
0.145 g (23%) of 5d was obtained as a red solid. M.p.
170 8C (dec.). Anal. Found: C, 30.56; H, 1.44. Calc. for
C32H14Fe6O18S2Se2: C, 30.91; H, 1.14%. IR (KBr disk,
cmꢁ1): n(CÅO) 2085(m), 2069(s), 2055(s), 2038(vs),
was stirred at 25ꢃ
/
30 8C for 0.5 h to give a yellowꢃbrown
/
solution containing approximately 1.0 mmol of the
[Et3NH]ꢀ salt of anion [(m-EtS)(m-CO)Fe2(CO)6]ꢁ. To
this solution was added 0.172 g (0.5 mmol) of m-
S2Fe2(CO)6 and the mixture was stirred at r.t. for 2 h
to give a brownꢃ
/
green solution. When this solution was
cooled to ꢁ78 8C, 0.05 ml (0.5 mmol) of SO2Cl2 was
/
added and the solution turned to red immediately. The
mixture was warmed to r.t. and stirred for an additional
2 h. Volatiles were removed in vacuo, and the residue
1
2022(s), 2006(s), 1992(vs). H NMR (CDCl3, d, ppm):
8.3 Hz, 8H,
2C6H4).
231 (s, 6H, 2CH3), 7.17 (q, AA?BB?, Jꢂ
/
was subjected to TLC. Petroleum ether/CH2Cl2 (v/vꢂ
/
20:1) eluted one major band, from which 0.158 g (31%)
of 5a was obtained as a red solid. M.p. 142 8C (dec.).
Anal. Found: C, 25.78; H, 0.97. Calc. for
C22H10Fe6O18S4: C, 25.75; H, 0.98%. IR (KBr disk,
cmꢁ1): n(CÅO) 2088(s), 2068(vs), 2035(vs), 2011(s),
3.9. Crystal X-ray structure determinations of 3b and 5b
Single-crystals of 3b and 5b suitable for X-ray
diffraction analysis were grown by slow evaporation of
their CH2Cl2/C6H14 solutions at about 4 8C. Each
crystal was mounted on a Bruker SMART 1000 or
1983(s). 1H NMR (CDCl3, d, ppm): 1.41 (t, Jꢂ
Hz, 6H, 2CH3), 2.50 (q, Jꢂ6.4 Hz, 4H, 2CH2).
/6.4
/
EnrafꢃNonius CAD-4 diffractometer with a graphite
/
˚
0.71073 A).
The structures were solved by direct methods and
3.6. Preparation of (m-t-BuS)2[Fe2(CO)6]3(m4-S)2
(5b)
monochromator with Mo Ka radiation (lꢂ
/
The same procedure as that for 5a was followed, but
approximately 1.0 mmol of the [Et3NH]ꢀ salt of anion
[(m-t-BuS)(m-CO)Fe2(CO)6]ꢁ [prepared from 0.504 g
(1.0 mmol) of Fe3(CO)12, 0.11 ml (1.0 mmol) of t-
BuSH and 0.14 ml (1.0 mmol) of Et3N] was employed in
place of approximately 1.0 mmol of the [Et3NH]ꢀ salt
of anion [(m-EtS)(m-CO)[Fe2(CO)6]ꢁ. 0.204 g (38%) of
5b was obtained as a red solid. M.p. 180 8C (dec.). Anal.
Found: C, 28.84; H, 1.71. Calc. for C26H18Fe6O18S4: C,
28.87; H, 1.68%. IR (KBr disk, cmꢁ1): n(CÅO) 2070(s),
Table 3
Crystal data and structural refinements details for 3b and 5b
3b
5b
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C27H10Fe6O19S4 C26H18Fe6O18S4
1101.69
293
triclinic
1081.76
299
monoclinic
C2/c (no. 15)
27.454(5)
9.303(2)
20.136(4)
90
¯
P1/
/
˚
a (A)
9.2239(9)
14.5729(13)
16.0294(15)
79.135(2)
74.749(2)
72.965(2)
1973.0(3)
2
˚
b (A)
˚
c (A)
1
2041(vs), 1989(vs), 1922(s). H NMR (CDCl3, d, ppm):
1.48 (s, 18H, 2(CH3)3C).
a (8)
b (8)
g (8)
V (A )
Z
Dcalc (g cmꢁ3
128.16(3)
90
3
˚
4044(2)
4
1.777
3.7. Preparation of (m-PhSe)2[Fe2(CO)6]3(m4-S)2 (5c)
)
1.854
2.433
1088
Absorption coefficient (mmꢁ1
F(000)
)
2.3627
2152
The same procedure as that for 5a was followed, but
approximately 1.5 mmol of the [Et3NH]ꢀ salt of anion
[(m-PhSe)(m-CO)Fe2(CO)6]ꢁ [prepared from 0.756 g (1.5
mmol) of Fe3(CO)12, 0.16 ml (1.5 mmol) of PhSeH and
0.23 ml (1.6 mmol) of Et3N] was employed in place of
approximately 1.0 mmol of the [Et3NH]ꢀ salt of anion
[(m-EtS)(m-CO)Fe2(CO)6]ꢁ. 0.072 g (12%) of 5c was
obtained as a red solid. M.p. 173 8C (dec.). Anal.
Found: C, 29.53; H, 1.06. Calc. for C30H10Fe6O18S2Se2:
C, 29.64; H, 0.83%. IR (KBr disk, cmꢁ1): n(CÅO) 2088(s),
Scan type
2umax (8)
Reflections collected
Independent reflections
Rint
v ꢃ
/
2u
v ꢃ2u
/
50.04
8244
6917
50.00
4002
3210
0.0309
SADABS
0.0524
0.1312
0.959
0.068
DIFABS
0.044
0.051
0.87
Absorption correction
R
Rw
Goodness-of-fit indicator
Largest difference peak and
0.641 and ꢁ
0.643
/
0.770 and ꢁ
0.550
/
1
ꢁ3
˚
hole (e A
2069(vs), 2040(vs), 1996(s). H NMR (CDCl3, d, ppm):
)
7.24ꢃ7.43 (m, 10H, 2C6H5).
/

18
L.-C. Song et al. / Inorganica Chimica Acta 346 (2003) 12ꢃ18
/
expanded by Fourier techniques. The final refinements
were accomplished by the full-matrix least-squares
method with anisotropic thermal parameters for non-
hydrogen atoms. Hydrogen atoms were located by using
the geometric method. The calculations were performed
References
[1] J.M. Coleman, A. Wojcicki, P.J. Pollick, L.F. Dahl, Inorg. Chem.
6 (1967) 1236.
[2] S.C. Carleton, F.G. Kennedy, S.A.R. Knox, J. Chem. Soc.,
Dalton Trans. (1981) 2230.
using SHELXTL-97 program for 3b and using the SDP
-
[3] C. Glidewell, A.R. Hyde, Inorg. Chim. Acta 87 (1984) L15.
[4] J.A. de Beer, R.J. Haines, J. Organomet. Chem. 24 (1970) 757.
[5] L.-C. Song, M. Kadiata, J.-T. Wang, R.-J. Wang, H.-G. Wang, J.
Organomet. Chem. 340 (1988) 239.
PLUS program for 5b. Details of the crystal data, data
collections and structure refinements are summarized in
Table 3.
[6] L.-C. Song, C.-G. Yan, Q.-M. Hu, R.-J. Wang, T.C.W. Mak, X.-
Y. Huang, Organometallics 15 (1996) 1535.
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4. Supplementary material
[8] L.-C. Song, G.-L. Lu, Q.-M. Hu, H.-T. Fan, Y. Chen, J. Sun,
Organometallics 18 (1999) 3258.
Crystallographic data for the structures reported in
this paper have been deposited with the Cambridge
Crystallographic Data Centre, CCDC Nos. 183210 and
183688 for compounds 3b and 5b, respectively. Copies
of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge, CB2
[9] L.-C. Song, Q.-M. Hu, H.-T. Fan, B.-W. Sun, M.-Y. Tang, Y.
Chen, Y. Sun, C.-X. Sun, Q.-J. Wu, Organometallics 19 (2000)
3909.
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1EZ, UK (fax: ꢀ44-1223-336-033; e-mail: deposit@
/
[12] D. Seyferth, G.B. Womack, J.C. Dewan, Organometallics 4
(1985) 398.
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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Organomet. Chem. 292 (1985) 9.
[14] R.B. King, Organometallic Syntheses; Transition-Metal Com-
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[15] D. Seyferth, R.S. Henderson, L.-C. Song, Organometallics 1
(1982) 125.
Acknowledgements
We are grateful to the National Natural Science
Foundation of China and State Key Laboratory of
Organometallic Chemistry for financial support.
[16] H. Gilman, E.A. Zoellner, J.B. Dickey, J. Am. Chem. Soc. 51
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