Synthesis of the novel thiolato-bridged and oxo-capped trimetallic clusters (η5-R′C5H4)(CO)2MFe 2(μ3-O)-(μ-RS)(CO)6 via reactions of [Et3NH][(μ-RS)(μ-CO)-Fe2</sub

Article abstract of DOI:10.1021/om980035w

The complex salts [Et₃NH][(μ-RS)(μ-CO)Fe₂(CO)₆] (1: R = Et, t-Bu, Ph), prepared from Fe₃(CO)₁₂, RSH, and Et₃N, react in situ with the triply bonded dimers [(η⁵-R′C₅H

Full text of DOI:10.1021/om980035w

3454
Organometallics 1998, 17, 3454-3459
Syn th esis of th e Novel Th iola to-Br id ged a n d Oxo-Ca p p ed
Tr im eta llic Clu ster s (η5-R′C5H4)(CO)2MF e2(µ3-O)-
(µ-RS)(CO)6 via Rea ction s of [Et3NH][(µ-RS)(µ-CO)-
F e2(CO)6] w ith Tr ip ly Bon d ed Dim er s
[(η5-R′C5H4)(CO)2M]2 (M ) Mo, W) a n d Su bsequ en t
Tr ea tm en t w ith Air . Cr ysta l Str u ctu r es of
(η5-MeO2CC5H4)(CO)2MoF e2(µ3-O)(µ-t-Bu S)(CO)6 a n d
(η5-EtO2CC5H4)(CO)2WF e2(µ3-O)(µ-EtS)(CO)6
Li-Cheng Song,*,† Hong-Tao Fan,† Qing-Mei Hu,† Xiang-Dong Qin,†
Wen-Feng Zhu,† Yu Chen,† and J ie Sun‡
Department of Chemistry, Nankai University, Tianjin 300071, China, and Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, China
Received J anuary 21, 1998
The complex salts [Et3NH][(µ-RS)(µ-CO)Fe2(CO)6] (1: R ) Et, t-Bu, Ph), prepared from
Fe3(CO)12, RSH, and Et3N, react in situ with the triply bonded dimers [(η5-R′C5H4)(CO)2M]2
(2: M ) Mo, W; R′ ) H, MeCO, MeO2C, EtO2C) followed by treatment with air to give the
series of novel clusters (η5-R′C5H4)(CO)2MoFe2(µ3-O)(µ-RS)(CO)6 (compound, R, R′: 3a , Et,
H; 3b, t-Bu, H; 3c, Et, MeCO; 3d , t-Bu, MeO2C; 3e, Ph, MeO2C; 3f, Et, EtO2C; 3g, t-Bu,
EtO2C; 3h , Ph, EtO2C) in 26-37% yields and (η5-R′C5H4)(CO)2WFe2(µ3-O)(µ-RS)(CO)6
(compound, R, R′: 3i, Et, MeO2C; 3j, t-Bu, MeO2C; 3k , Et, EtO2C) in 12-17% yields. Single-
crystal X-ray diffraction analyses of 3d and 3k confirmed that (i) these clusters consist of
the M-S (M ) Mo, W) edge-opened square-pyramidal cluster skeleton MFe2SO with the M
atom occupying its apical position and the Fe2OS atoms constructing its pyramid base and
(ii) clusters 3d and 3k are single isomers in which the t-Bu and Et groups are bonded to the
bridged S atoms by an equatorial type of bond.
In tr od u ction
carried out an investigation on the reactions of 1 with
the inorganic acetylene analogues [(η5-R′C5H4)(CO)2M]2
(2, M ) Mo, W) followed by treatment with air.
Consequently, these reactions afforded a series of novel
thiolato-bridged, oxo-capped trimetallic clusters (η5-
R′C5H4)(CO)2MFe2(µ3-O)(µ-RS)(CO)6 (3a -k ), as de-
scribed below.
In recent years the chemical reactions of diiron
complex salts [Et3NH][(µ-RS)(µ-CO)Fe2(CO)6] (1) have
been intensively studied and widely utilized in the
synthesis of organometallic compounds and particularly
organometallic clusters.1-9 Among the reactions studied
were those with electrophiles that have no leaving group
such as acetylenes and elemental sulfur.3,4 As part of
our project concerning the chemistry of the anions [(µ-
RE)(µ-CO)Fe2(CO)6]- (E ) S, Se, Te),8-10 we recently
Resu lts a n d Discu ssion
Syn th esis of (η5-R′C5H4)(CO)2MF e2(µ3-O)(µ-RS)-
(CO)6 (3a -k ). When salts of the type [Et3NH][(µ-RS)-
(µ-CO)Fe2(CO)6] (1: R ) Et, t-Bu, Ph) (prepared from
Fe3(CO)12, RSH, and Et3N) reacted with the triply
bonded dimers [(η5-R′C5H4)(CO)2M]2 (2: M ) Mo, W;
R′ ) H, MeCO, MeO2C, EtO2C) followed by bubbling
air into the reaction mixture in THF at room temper-
ature, and after open-air TLC separation, the clusters
(η5-R′C5H4)MFe2(µ3-O)(µ-RS)(CO)6 (3a -k ) were isolated,
in addition to the two minor byproducts (µ-RS)2Fe2(CO)6
and [(η5-R′C5H4)(CO)3M]2 (Scheme 1).
The former byproducts (µ-RS)2Fe2(CO)6 are commonly
obtained in the reactions involving 1. The latter
byproducts, singly bonded dimers, usually were obtained
in the reactions of 2 and probably were derived by
addition of CO evolved from 1 and/or 2 to the triple bond
† Nankai University.
‡ Shanghai Institute of Organic Chemistry.
(1) Seyferth, D.; Womack, G. B.; Dewan, J . C. Organometallics 1985,
4, 398.
(2) Seyferth, D.; Hoke, J . B.; Dewan, J . C. Organometallics 1987, 6,
895.
(3) Seyferth, D.; Womack, G. B.; Archer, C. M.; Fackler, J . P., J r.;
Marler, D. O. Organometallics 1989, 8, 443.
(4) Seyferth, D.; Hoke, J . B.; Womack, G. B. Organometallics 1990,
9, 2662.
(5) Seyferth, D.; Anderson, L. L.; Davis, W. M. J . Organomet. Chem.
1993, 459, 271.
(6) Seyferth, D.; Ruschke, D. P.; Davis, W. M.; Cowie, M.; Hunter,
A. D. Organometallics 1994, 13, 3834.
(7) Delgado, E.; Hernandez, E.; Rossel, O.; Seco, M.; Puebia, E. G.;
Ruiz, C. J . Organomet. Chem. 1993, 455, 177.
(8) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Wang, R.-J .; Mak, T. C. W.;
Huang, X.-Y. Organometallics 1996, 15, 1535 and references therein.
(9) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Wu, B.-M.; Mak, T. C. W.
Organometallics 1997, 16, 632 and references therein.
(10) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Huang, X.-Y. Organometal-
lics 1997, 16, 3769 and references therein.
S0276-7333(98)00035-1 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 07/09/1998

Thiolato-Bridged, Oxo-Capped Trimetallic Clusters
Organometallics, Vol. 17, No. 16, 1998 3455
Sch em e 1
Ta ble 1. Yield s (%) of 3a -k Obta in ed by Tw o
Ta ble 2. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for 3d
P r oced u r es
3a 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k
Mo(1)-Fe(1)
Mo(1)-O(11)
Mo(1)-C(2)
C(13)-C(14)
C(14)-O(9)
S(1)-C(16)
Fe(2)-C(6)
Fe(2)-O(11)
2.735(2)
1.975(3)
1.970(6)
1.467(8)
1.329(7)
1.890(6)
1.783(6)
1.936(3)
Mo(1)-Fe(2)
Mo(1)-C(1)
Mo(1)-C(9)
C(14)-O(10)
Fe(1)-S(1)
Fe(1)-C(3)
Fe(1)-O(11)
Fe(2)-S(1)
2.7405(9)
1.960(6)
2.350(5)
1.196(7)
2.316(2)
1.797(6)
1.936(3)
2.332(2)
from first proc
32 33 26 35 37 37 27 35 17 13 12
From second proc 17 19 16 26 21 16 16 19
4
5
6
of 2.11-13 While (µ-RS)2Fe2(CO)6 and [(η5-R′C5H4)-
(CO)3M]2 produced in this study are known, the prod-
ucts 3a -k are new; they are deeply colored, air-stable
solids and have been fully characterized by elemental
analysis, spectroscopy, and X-ray crystallography.
Fe(1)-Mo(1)-Fe(2) 69.40(2) Fe(1)-Mo(1)-O(11) 45.03(10)
Fe(1)-Mo(1)-C(1) 65.7(2) Fe(2)-Mo(1)-C(2) 65.2(2)
Mo(1)-Fe(1)-O(11) 46.22(10) Mo(1)-Fe(2)-O(11) 46.11(10)
At present, we do not know clearly about the mech-
anism for production of 3a -k . However, it is apparent
that for formation of 3a -k from this procedure the
structural units R′C5H4(CO)2M and RSFe2(CO)6 were
derived from 1 and 2, respectively, and the µ3-O atom
coordinated to the three metals MFe2 originated most
likely from the oxygen of bubbling air. In addition, we
found that 3a -k could also be prepared by another
procedure, which includes reactions of 1 with 2 without
subsequently bubbling air but is followed directly by an
open-air TLC separation. In this procedure the µ3-O
atoms in 3a -k most likely originated from the oxygen
present in air during the course of open-air TLC
separation. For comparison, Table 1 lists the yields of
3a -k prepared by two such procedures. As can be seen,
the yields of 3a -k from the first procedure (with
bubbling air plus open-air TLC) are much higher than
those from the second procedure (without bubbling air
but with only open-air TLC).
It is worth pointing out that in the first procedure
the 0.5 h of air-bubbling time is optimal for preparation
of 3a -k and extending the air-bubbling time generally
leads to a decrease in their yields. For example, for 3d
the yield is 35% for 0.5 h of air bubbling, whereas yields
of 3d are respectively 30% and 27% for 1 and 2 h of air
bubbling, possibly due to the composition of 3d to a
certain degree in the prolonged presence of air. In
addition, we found that, in contrast to the second
procedure, separation of the products by TLC in an
anaerobic drybox, instead of open-air TLC separation,
gave only a trace of 3a -k , which further supports the
source of µ3-O in 3a -k being from the oxygen of air. In
Mo(1)-Fe(1)-S(1)
Fe(1)-S(1)-Fe(2)
83.48(5) Mo(1)-Fe(2)-S(1)
84.23(5) Fe(1)-S(1)-C(16) 118.0(2)
83.08(4)
Fe(2)-S(1)-C(16) 119.3(2)
O(9)-C(14)-O(10) 123.0(6)
C(13)-C(14)-O(10) 124.1(6)
166.6(5)
Mo(1)-C(1)-O(1)
Mo(1)-C(2)-O(2)
167.5(5)
Fe(1)-O(11)-Fe(2) 107.3(2)
Mo(1)-O(11)-Fe(2) 88.9(1)
Mo(1)-O(11)-Fe(1) 88.7(1)
fact, in the presence of air the reactions involving
transition metal complexes usually yield products con-
taining oxygen atoms such as Cp2Mo2O2(µ-Te)(µ-NPh),14
Cp2Mo2O2(µ-O)(µ-E)(E ) S, Te),15 and (η5-C5Me5)2Mo2-
Fe2(CO)7(µ3-O),16 in which the oxygen atoms are bonded
to transition metals in terminal, bridged, and capped
coordination manners.
Molecu la r Str u ctu r es of 3d a n d 3k . To confirm
the structures of compounds 3a -k , the single-crystal
diffraction analyses of two representative compounds
3d and 3k were undertaken. Significant bond lengths
and angles for each structure are listed in Tables 2 and
3, respectively. ORTEP plots of each are shown in
Figures 1 and 2, respectively.
As can be seen from Figures 1 and 2, the molecules
of 3d and 3k contain an M-S edge-opened square-
pyramidal skeleton MFe2OS (M ) Mo, W) with the M
atom as its top and a planar Fe2OS as its base. The
MFe2OS skeleton, wherein the oxygen atom is µ3-
coordinated to MFe2 atoms, has one substituted cyclo-
pentadienyl ligand and two CO ligands coordinated to
the M atom, two sets of three CO ligands coordinated
to two Fe atoms, and one t-Bu or Et group bound to the
S atom bridged between two Fe atoms. 3d and 3k are
typical examples of 50-electron clusters which, according
to the 18-electron rule, should possess two Mo-Fe or
two W-Fe metal-metal single bonds. This is consistent
(11) Song, L.-C.; Wang, J .-Q.; Hu, Q.-M.; Huang, X.-Y. Polyhedron
1997, 16, 2249.
(12) Song, L.-C.; Wang, J .-Q.; Zhao, W.-J .; Hu, Q.-M.; Fan, Y.-Q.;
Zhang, S.-J .; Wang, R.-J .; Wang, H.-G. J . Organomet. Chem. 1993, 453,
105.
(14) Mathur, P.; Ghose, S.; Hossain, Md. M.; Vahrenkamp, H. J .
Organomet. Chem. 1997, 538, 185.
(15) Mathur, P.; Ghose, S.; Hossain, Md. M.; Hitchcock, P. B.; Nixon,
J . F. J . Organomet. Chem. 1997, 542, 265.
(13) Song, L.-C.; Shen, J .-Y.; Wang, J .-Q.; Hu, Q.-M.; Wang, R.-J .;
Wang, H.-G. Polyhedron 1994, 13, 3235.
(16) Gibson, C. P.; Huang, J .-S.; Dahl, L. F. Organometallics 1986,
5, 1676.

3456 Organometallics, Vol. 17, No. 16, 1998
Song et al.
F igu r e 2. ORTEP view of 3k with atom-labeling scheme.
3k are 1.950(3), 2.307(1), and 1.942(3) Å, respectively.
The dihedral angles between two planes of the Fe2OS
base and the Cp ring are 56.23 and 56.04° in 3d and
3k , respectively. To our knowledge, such an open-
pyramid MFe2OS skeleton has never been found in
transition-metal/main-group-element clusters, so far.
Among the eight carbonyl ligands attached to metals
of the skeleton, two carbonyls bound to the Mo or W
atom are semibridging and the others attached to Fe
atoms are terminal. For semibridging carbonyls Cur-
tis’s definition19 is 0.1 e d ) (d2 - d1)/d1 e 0.6. For
C(1)O(1) of 3d , since d2 ) Fe(1)‚‚‚C(1) ) 2.629(6) Å and
d1 ) Mo(1)-C(1) ) 1.960(6) Å, RC(1)O(1) ) 0.34. For
C(2)O(2) of 3d , since d2 ) Fe(2)‚‚‚C(2) ) 2.618(6) Å and
d1 ) Mo(1)-C(2) ) 1.970(6) Å, RC(2)O(2) ) 0.33. They
both fall into the R range for semibridging carbonyls.
In addition, since the angles Fe(1)Mo(1)C(1) ) 65.7(2)°
and Fe(2)Mo(1)C(2) ) 65.2(2)°, C(1)O(1) and C(2)O(2)
are bridges across the Mo(1)Fe(1) and Mo(1)Fe(2) bonds,
respectively. Similarly, for 3k the R values for semibridg-
ing carbonyls C(1)O(2) and C(2)O(3) can be calculated
as 0.33 and 0.35. The two carbonyls are bridges across
the WFe(1) and WFe(2) bonds, since the angles Fe(1)-
WC(1) and Fe(2)WC(2) are 65.0(1) and 66.2(1)°, respec-
tively. For the substituted cyclopentadienyl ligands the
distance Mo‚‚‚Cp ring centroid ) 2.034 Å in 3d is almost
the same as the distance W‚‚‚Cp ring centroid ) 2.023
Å in 3k . The bond lengths C(13)C(14) (1.467(8) and
1.492(7) Å) in 3d and 3k are much shorter than a
normal C-C single bond; thus, the π-systems of the
substituents should be quite well conjugated with the
Cp ring π-systems of 3d and 3k . To see clearly the
orientations of t-Bu and Et groups, condensed ORTEP
drawings of 3d and 3k in which their eight CO carbo-
F igu r e 1. ORTEP view of 3d with atom-labeling scheme.
Ta ble 3. Selected Bon d Len gth s (Å) a n d Bon d
An gles (d eg) for 3k
Fe(1)-W
2.7447(7)
1.942(3)
1.965(5)
2.302(1)
1.952(3)
1.801(6)
1.492(7)
1.317(6)
Fe(2)-W
W-C(1)
2.7404(6)
1.959(4)
2.312(1)
1.949(3)
1.801(6)
1.818(5)
1.194(6)
2.338(4)
W-O(1)
W-C(2)
Fe(2)-S
Fe(2)-O(1)
Fe(2)-C(6)
C(13)-C(14)
C(14)-O(11)
Fe(1)-S
Fe(1)-O(1)
Fe(1)-C(3)
S-C(17)
C(14)-O(10)
W-C(9)
Fe(1)-W-Fe(2)
Fe(1)-W-C(1)
Fe(2)-W-O(1)
W-Fe(1)-S
69.25(2) Fe(1)-W-O(1)
65.0(1) C(9)-W-C(1)
45.42(8) W-Fe(1)-O(1)
82.72(3) W-Fe(1)-C(3)
83.01(3) W-Fe(2)-O(1)
45.23(8)
83.9(2)
45.02(8)
88.9(2)
45.11(8)
84.98(4)
110.7(2)
168.2(4)
W-Fe(2)-S
W-Fe(2)-C(7)
Fe(1)-S-C(17)
W-C(1)-O(2)
O(10)-C(14)-O(11) 126.2(5)
W-O(1)-Fe(1) 89.7(1)
120.7(2)
113.5(2)
167.3(4)
Fe(1)-S-Fe(2)
Fe(2)-S-C(17)
W-C(2)-O(3)
O(10)-C(14)-C(13) 123.1(5)
Fe(1)-O(1)-Fe(2) 106.1(1)
with the bond lengths of Mo-Fe(2.735(2), 2.7405(9) Å)
in 3d and W-Fe (2.7447(7), 2.7404(6) Å) in 3k , which
are comparable to Mo-Fe and W-Fe single-bond lengths
in similar Mo/Fe- and W/Fe-containing compounds.16,17
The nonbonding distances between two Fe atoms in 3d
and 3k are 3.118 and 3.116 Å, respectively, which fall
well out of the range for normal single Fe-Fe bond
lengths.18 For the planar pyramid base Fe2OS, the bond
lengths of Fe-O (average), Fe-S (average), and Mo-O
in 3d are 1.936(3), 2.324(2), and 1.975(3) Å, whereas
those of Fe-O (average), Fe-S (average), and W-O in
(17) Song, L.-C.; Shen, J .-Y.; Hu, Q.-M.; Huang, X.-Y. Organome-
tallics 1995, 14, 98.
(18) (a) Chieh, C.; Seyferth, D.; Song, L.-C. Organometallics 1982,
1, 473. (b) Wei, C.-H.; Dahl, L. F. Inorg. Chem. 1965, 4, 1.
(19) Curtis, M. D.; Han, K. R.; Butler, W. M. Inorg. Chem. 1980,
19, 2096.

Thiolato-Bridged, Oxo-Capped Trimetallic Clusters
Organometallics, Vol. 17, No. 16, 1998 3457
one triplet at δ 1.10 and one quartet at δ 2.40 for Et,
whereas that of 3b exhibits two singlets at δ 5.28 and
5.47 for its Cp ring and two singlets at δ 1.30 and 1.40
for its t-Bu group. This implies that 3a consists of an
single isomer but 3b is a mixture of two isomers.21,22
For 3a the isomer should have an equatorial Et (δ(CH2)
2.40, δ(CH3) 1.10),21 whereas for 3b one isomer should
have an equatorial t-Bu (δ 1.40) and the other should
have an axial t-Bu (δ 1.30).23 For the other products
3c-k the four protons on substituted Cp rings show two
sets of signals at about δ 6.7 and 5.5. The set of signals
at higher field is assigned to H3 and H4 protons remote
from the substituent, whereas the set of signals at lower
field is ascribed to H2 and H5 protons close to the
substituent, since the substituents are electron-with-
1
drawing groups.24 In addition, the H NMR spectra of
organic groups R attached to the bridged sulfur atoms
show one singlet at about δ 7.3 for Ph and at about δ
1.3 for t-Bu and one triplet at about δ 1.1 and one
quartet at about δ 2.4 for Et. This implies that products
3c-k consist of an single isomer, which should have the
R groups attached to the bridged S atoms by an
equatorial type of bond.20-22 Such isomer assignments,
similar to those for 3a ,b, were primarily made on the
F igu r e 3. Condensed ORTEP drawing of 3d .
1
basis of the H NMR data of R groups attached to the
bridged sulfur atom and the structure similarity be-
tween (µ-RS)2Fe2(CO)6 and 3a ,k , both of which have a
butterfly skeleton of Fe2S2 or MFe2S (see the single-
crystal structures described above).22,23
Exp er im en ta l Section
All reactions were carried out under prepurified tank
nitrogen using standard Schlenk or vaccum-line techniques.
Tetrahydrofuran (THF) was distilled from sodium-benzophe-
none ketyl, while triethylamine was distilled from potassium
hydroxide under nitrogen. Mercaptans RSH (R ) Et, t-Bu,
Ph) were of commercial origin and used without further
purification. Triiron dodecacarbonyl,25 [(η5-R′C5H4)(CO)2Mo]2
(R′ ) H, MeCO, MeO2C, EtO2C),13,26 and [(η5-R′C5H4)W(CO)2]2
(R′ ) MeO2C, EtO2C)12 were prepared according to literature
procedures. Products 3a -k were purified by open-air chro-
matography (silica gel G 10-40 µm); the second band sepa-
rated with ease from the first band of the least polar byprod-
ucts (µ-RS)2Fe2(CO)6 but with diffculty (particular for the
tungsten homologues 3i-k ) from the third band of byproducts
[(η5-RC5H4)(CO)3M]2 due to their very close polarity. The
products for analyses were further purified by recrystallization
from petroleum ether/CH2Cl2. IR and 1H NMR spectra were
recorded on a Nicolet FT-IR 5DX infrared spectrophotometer
and a J eol FX-90Q NMR spectrometer, respectively. C/H
analyses were performed on a Perkin-Elmer Model 240C
analyzer. Melting points were determined on a Yanaco MP-
500 apparatus and were uncorrected.
F igu r e 4. Condensed ORTEP drawing of 3k .
nyls are omitted are shown in Figures 3 and 4. As easily
seen from Figures 3 and 4, the t-Bu group of 3d and
the Et group of 3k lie in an equatorial, not axial,
position20 relative to the oxo-capped MFe2S butterfly
skeleton.
Sp ectr oscop ic Ch a r a cter iza tion of 3a -k . In ad-
dition to the X-ray single-crystal structures of 3d and
3k , the IR and 1H NMR spectra of 3a -k were also
determined. The IR spectra of 3a -k show five to six
strong absorption bands in the range 2090-1815 cm-1
,
characteristic of the terminal and semibridging carbo-
nyls attached to Fe and Mo/W atoms, respectively. This
is consistent with the results of single-crystal diffraction
analyses for 3d and 3k . In addition, the IR spectrum
of 3c shows one strong absorption band at 1688 cm-1
for its ketonic carbonyl, whereas those of 3d -k exhibit
one strong band at 1704-1737 cm-1 for their ester
P r ep a r a tion s of 3a -k by th e F ir st P r oced u r e. P r ep a -
r a tion of (η5-C5H5)(CO)2MoF e2(µ3-O)(µ-EtS)(CO)6 (3a ). A
100 mL three-necked flask equipped with a magnetic stirbar,
a rubber septum, and a nitrogen inlet tube was charged with
(21) King, R. B. J . Am. Chem. Soc. 1963, 85, 1584.
(22) Seyferth, D.; Henderson, R. S.; Song, L.-C. Organometallics
1982, 1, 125.
(23) De Beer, J . A.; Haines, R. J . J . Organomet. Chem. 1970, 24,
757.
(24) Macomber, D. W.; Rausch, M. D. J . Organomet. Chem. 1983,
258, 331.
(25) King, R. B. Organometallic Syntheses; Academic Press: New
York, 1965; Vol. 1 (Transition-Metal Compounds), p 95.
(26) Curtis, M. D.; Fotinos, N. A.; Messerle, L.; Sattelberger, A. P.
Inorg. Chem. 1983, 22, 1559.
1
carbonyls. The H NMR spectra of 3a -k indicate the
presence of their respective R and R′ organic groups.
For example, for 3a ,b, the 1H NMR spectrum of 3a
shows one singlet at δ 5.80 for its parent Cp ring and
(20) Shaver, A.; Fitzpatrick, P. J .; Steliou, K.; Butler, I. S. J . Am.
Chem. Soc. 1979, 101, 1313.

3458 Organometallics, Vol. 17, No. 16, 1998
Song et al.
1.00 g (1.98 mmol) of Fe3(CO)12 and 30 mL of THF. To the
resulting green solution were added 0.16 mL (2 mmol) of EtSH
and 0.28 mL (2 mmol) of Et3N, and the mixture was stirred
at room temperature for about 0.5 h to give a brown solution
of [Et3NH][(µ-EtS)(µ-CO)Fe2(CO)6]. To this solution was added
0.43 g (1.0 mmol) of [(η5-C5H5)(CO)2Mo]2, and the mixture was
stirred at room temperature for 0.5 h under a bubbling stream
of N2. The N2 stream was then changed to an air stream,
which was bubbled into the reaction mixture at room temper-
ature for 0.5 h. Solvent was removed at reduced pressure. The
residue was subjected to open-air TLC separation using 10:1
(v/v) petroleum ether/acetone as eluent. The first and third
bands were identified as the known compounds (µ-EtS)2Fe2(CO)6
and [η5-C5H5(CO)3Mo]2, in small quantities. From the second
band was obtained 184 mg (32%) of 3a as a yellow-green solid.
3a : mp 105 °C dec. Anal. Calcd for C15H10Fe2MoO9S: C,
31.39; H, 1.76. Found: C, 31.00; H, 1.42. IR (KBr, disk): νCt
Fe2(CO)6] was added 0.58 g (1.0 mmol) of [(η5-EtO2CC5H4)(CO)2-
Mo]2. After removal of small amounts of (µ-EtS)2Fe2(CO)6 and
[(η5-EtO2CC5H4)(CO)3Mo]2, 240 mg (37%) of 3f was obtained
as a deep green solid. 3f: mp 138 °C dec. Anal. Calcd for
C18H14Fe2MoO11S: C, 33.47; H, 2.18. Found: C, 33.40; H, 1.97.
IR (KBr, disk): νCtO 2070 (s), 2054 (s), 1999 (vs), 1971 (vs),
1889 (s), 1839 (s); νCdO 1723 (s) cm-1
.
1H NMR (CDCl3): δ
1.04 (t, J ) 7.2 Hz, 3H, SCH2CH3), 1.40 (t, J ) 7.2 Hz, 3H,
OCH2CH3), 2.32 (q, J ) 7.2 Hz, 2H, SCH2), 4.39 (q, J ) 7.2
Hz, 2H, OCH2), 5.46 (t, 2H, H3, H4), 6.60 (t, 2H, H2, H5) ppm.
P r ep a r a tion of (η5-EtO2CC5H4)(CO)2MoF e2(µ3-O)(µ-t-
Bu S)(CO)6 (3g). To a solution of [Et3NH][(µ-t-BuS)(µ-CO)-
Fe2(CO)6] was added 0.58 g (1.0 mmol) of [η5-EtO2CC5H4(CO)2-
Mo]2. After removal of small amounts of the known compounds
(µ-t-BuS)2Fe2(CO)6 and [(η5-EtO2CC5H4)(CO)3Mo]2, 184 mg
(27%) of 3g was obtained as a deep green solid. 3g: mp 135
°C dec. Anal. Calcd for C20H18Fe2MoO11S: C, 35.64; H, 2.69.
Found: C, 35.64; H, 2.88. IR (KBr, disk): νCtO 2072 (s), 2049
2073 (s), 2049 (vs), 1991 (vs), 1868 (s), 1819 (s) cm-1
.
1H
O
NMR (CDCl3): δ 1.10 (t, J ) 7.2 Hz, 3H, CH3), 2.40 (q, J )
7.2 Hz, 2H, CH2), 5.80 (s, 5H, C5H5) ppm.
(vs), 1983 (vs), 1885 (s), 1844 (s); νCdO 1721 (s) cm-1 1H NMR
.
(CDCl3): δ1.32 (s, 9H, t-C4H9), 1.47 (t, J ) 7.2 Hz, 3H, CH3),
4.45 (q, J ) 7.2 Hz, 2H, CH2), 5.48 (t, 2H, H3, H4), 6.70 (t, 2H,
H2, H5) ppm.
P r ep a r a t ion of (η5-C5H5)(CO)2MoF e2(µ3-O)(µ-t-Bu S)-
(CO)6 (3b). The same procedure was used as that for
preparation of 3a . To a solution of [Et3NH][(µ-t-BuS)(µ-CO)-
Fe2(CO)6] prepared from 0.28 mL (2 mmol) of t-BuSH was
added 0.44 g (1.0 mmol) of [(η5-C5H5)(CO)2Mo]2. After removal
of small amounts of the known compounds (µ-t-BuS)2Fe2(CO)6
and [(η5-C5H5)(CO)3Mo]2, 200 mg (33%) of 3b was obtained as
a deep green solid. 3b: mp 121-122 °C. Anal. Calcd for
P r ep a r a tion of (η5-EtO2CC5H4)(CO)2MoF e2(µ3-O)(µ-P h -
S)(CO)6 (3h ). To a solution of [Et3NH][(µ-PhS)(µ-CO)-
Fe2(CO)6] was added 0.58 g (1.0 mmol) of [(η5-EtO2CC5H4(CO)2-
Mo]2. After removal of small amounts of the known compounds
(µ-PhS)2Fe2(CO)6 and [(η5-EtO2CC5H4(CO)3Mo]2, 240 mg (35%)
of 3h was obtained as a deep-brown solid. 3h : mp 124 °C
dec. Anal. Calcd for C22H14Fe2MoO11S: C, 38.07; H, 2.03.
Found: C, 37.82; H, 2.09. IR (KBr, disk): νCtO 2090 (s), 2057
C
17H14Fe2MoO9S: C, 33.91; H, 2.34. Found: C, 33.73; H, 2.28.
IR (KBr, disk): νCtO 2051 (s), 2021 (vs), 1980 (vs), 1926 (s),
1835 (s) cm-1 1H NMR (CDCl3): δ 1.30,1.40 (s, s, 9H, t-C4H9),
.
(vs), 2000 (vs), 1868 (s), 1827 (s); νCdO 1704 (s) cm-1 1H NMR
.
(CDCl3): δ 1.44 (t, J ) 7.2 Hz, 3H, CH3), 4.46 (t, J ) 7.2 Hz,
2H, CH2), 5.58 (t, 2H, H3, H4), 6.70 (t, 2H, H2, H5), 7.30 (s, 5H,
C6H5) ppm.
5.28, 5.47 (s, s, 5H, C5H5) ppm.
P r ep a r a t ion of (η5-MeCOC5H 4)(CO)2MoF e2(µ3-O)(µ-
EtS)(CO)6 (3c). To a solution of [Et3NH][(µ-EtS)(µ-CO)Fe2-
(CO)6] was added 0.55 g(1.0 mmol) of [(η5-MeCOC5H4)(CO)2-
Mo]2. After removal of small amounts of the known compounds
(µ-EtS)2Fe2(CO)6 and [(η5-MeCOC5H4)(CO)3Mo]2, 160 mg (26%)
of 3c was obtained as a deep green solid. 3c: mp 143 °C dec.
Anal. Calcd for C17H12Fe2MoO10S: C, 33.14; H, 1.96. Found:
C, 33.26; H, 1.89. IR (KBr, disk): νCtO 2080 (s), 2057 (s), 2023
P r epar ation of (η5-MeO2CC5H4)(CO)2WFe2(µ3-O)(µ-EtS)-
(CO)6 (3i). To a solution of [Et3NH][(µ-EtS)(µ-CO)Fe2(CO)6]
was added 0.73 g (1.0 mmol) of [(η5-MeO2CC5H4)(CO)2W]2.
After removal of small amounts of the known compounds (µ-
EtS)2Fe2(CO)6 and [(η5-MeO2CC5H4)(CO)3W]2, 120 mg (17%)
of 3i was obtained as a deep green solid. 3i: mp 127-128 °C.
Anal. Calcd for C17H12Fe2O11SW: C, 28.36; H, 1.68. Found:
C, 28.37; H, 1.67. IR (KBr, disk): νCtO 2079 (s), 2053 (vs),
(vs), 2004 (vs), 1981 (s), 1869 (s); νCdO 1688 (m) cm-1 1H NMR
.
(CDCl3): δ 1.11 (t, J ) 7.2 Hz, 3H, CH3), 2.34 (q, J ) 7.2 Hz,
2H, CH2), 2.52 (s, 3H, CH3CO), 5.39 (br s, 2H, H3, H4), 6.66
(br s, 2H, H2, H5) ppm.
1
1991 (vs), 1972 (vs), 1869 (s), 1815 (s); νCdO 1729 (s) cm-1. H
NMR (CDCl3): δ 1.16 (t, J ) 7.2 Hz, 3H, CH3), 2.38 (q, J )
7.2 Hz, 2H, CH2), 3.94 (s, 3H, OCH3), 5.65 (t, 2H, H3, H4), 6.72
(t, 2H, H2, H5) ppm.
P r ep a r a tion of (η5-MeO2CC5H4)(CO)2MoF e2(µ3-O)(µ-t-
Bu S)(CO)6 (3d ). To a solution of [Et3NH][(µ-t-BuS)(µ-CO)-
Fe2(CO)6] was added 0.55 g (1.0 mmol) of [(η5-MeO2CC5H4)(CO)2-
Mo]2. After removal of small amounts of known compounds
(µ-t-BuS)2Fe2(CO)6 and [η5-MeO2CC5H4(CO)3Mo]2, 230 mg
(35%) of 3d was obtained as a deep green solid. If air was
bubbled for 1 h or for 2 h, 200 mg (30%) or 180 mg (27%) of 3d
was obtained, respectively. 3d : mp 110 °C dec. Anal. Calcd
for C19H16Fe2MoO11S: C, 34.58; H, 2.44. Found: C, 34.39; H,
2.38. IR (KBr, disk): νCtO 2073 (s), 2049 (vs), 1983 (vs), 1877
P r ep a r a tion of (η5-MeO2CC5H4)(CO)2WF e2(µ3-O)(µ-t-
Bu S)(CO)6 (3j). To a solution of [Et3NH][(µ-t-BuS)(µ-CO)-
Fe2(CO)6] was added 0.73 g (1.0 mmol) of [(η5-MeO2CC5H4)-
(CO)2W]2. After removal of small amounts of the known
compounds (µ-t-BuS)2Fe2(CO)6 and [(η5-MeO2CC5H4)(CO)3W]2,
96 mg (13%) of 3j was obtained as a deep green solid. 3j: mp
130-132 °C. Anal. Calcd for C19H16Fe2O11SW: C, 30.51; H,
2.16. Found: C, 30.34; H, 2.26. IR (KBr, disk): νCtO 2071
(vs), 1836 (s); νCdO 1721 (s) cm-1 1H NMR (CDCl3): δ 1.32 (s,
.
(s), 2044 (vs), 1991 (vs), 1881 (s), 1825 (s); νCdO 1737 (s) cm-1
.
9H, t-C4H9), 3.96 (s, 3H, OCH3), 5.46 (t, 2H, H3, H4), 6.66 (t,
2H, H2, H5) ppm.
1H NMR (CDCl3): δ 1.30 (s, 9H, t-C4H9), 3.92 (s, 3H, OCH3),
5.48 (t, 2H, H3, H4), 6.76 (t, 2H, H2, H5) ppm.
P r ep a r a t ion of (η5-MeO2CC5H 4)(CO)2MoF e2(µ3-O)(µ-
P h S)(CO)6 (3e). To a solution of [Et3NH][(µ-PhS)(µ-CO)Fe2-
(CO)6] prepared from 0.2 mL (2 mmol) of PhSH was added
0.55 g(1.0 mmol) of [(η5-MeO2CC5H4)(CO)2Mo]2. After removal
of amounts of the known compounds (µ-PhS)2Fe2(CO)6 and [(η5-
MeO2CC5H4)(CO)3Mo]2, 248 mg (37%) of 3e was obtained as a
5
P r ep a r a tion of (η -EtO2CC5H4)(CO)2WF e2(µ3-O)(µ-EtS)-
(CO)6 (3k ). To a solution of [Et3NH][(µ-EtS)(µ-CO)Fe2(CO)6]
was added 0.75 g(1.0 mmol) of [(η5-EtO2CC5H4(CO)2W]2. After
removal of small amounts of the known compounds (µ-
EtS)2Fe2(CO)6 and [(η5-EtO2CC5H4(CO)3W]2, 88 mg (12%) of
3k was obtained as a deep green solid. 3k : mp 120-122 °C.
Anal. Calcd for C18H14Fe2O11SW: C, 29.46; H, 1.92. Found:
C, 29.20; H, 2.10. IR (KBr, disk): νCtO 2070 (s), 2052 (vs),
deep green solid. 3e: mp 119-121 °C. Anal. Calcd for C21H12
-
Fe2MoO11S: C, 37.09; H, 1.78. Found: C, 37.02; H, 1.40. IR
(KBr, disk): νCtO 2082 (s), 2049 (s), 2000 (vs), 1975 (s), 1877
(s), 1827 (m); νCdO 1721 (s) cm-1 1H NMR (CDCl3): δ 3.92 (s,
.
1988 (vs), 1970 (s), 1882 (s), 1829 (s); νCdO 1725 (s) cm-1 1H
.
3H, OCH3), 5.56 (t, 2H, H3, H4), 6.64 (t, 2H, H2, H5), 7.28 (s,
5H, C6H5) ppm.
NMR (CDCl3): δ 1.08 (t, J ) 7.2 Hz, 3H, SCH2CH3), 1.41 (t, J
) 7.2 Hz, 3H, OCH2CH3), 2.38 (q, J ) 7.2 Hz, 2H, SCH2), 4.40
(q, J ) 7.2 Hz, 2H, OCH2), 5.64 (t, 2H, H3, H4), 6.76 (t, 2H, H2,
H5) ppm.
P r ep a r a t ion of (η5-E t O2CC5H 4)(CO)2MoF e2(µ3-O)(µ-
EtS)(CO)6 (3f). To a solution of [Et3NH][(µ-EtS)(µ-CO)-

Thiolato-Bridged, Oxo-Capped Trimetallic Clusters
Organometallics, Vol. 17, No. 16, 1998 3459
Ta ble 4. Cr ysta l Da ta Collection a n d Refin em en t for 3d a n d 3k
3d
3k
mol formula
mol wt
C
19H16Fe2MoO11
S
C18H14Fe2O11SW
733.91
660.02
cryst syst
space group
a, Å
b, Å
orthorhombic
P212121 (No. 19)
9.684(7)
27.84(2)
8.815(1)
triclinic
P1h (No. 2)
8.9875(8)
18.179(4)
7.3216(8)
94.45(1)
101.345(8)
98.35(1)
1154.6(3)
2
c, Å
R, deg
â, deg
γ, deg
V, Å3
2376(2)
4
1.844
Z
density (calcd), g cm-3
2.111
F(000)
1312
18.66
Rigaku AFC7R
20
704
63.59
Rigaku AFC7R
20
µ(Mo KR), cm-1
diffractometer
temp, °C
radiation
scan type
2θmax, deg
no. of observns, n
Mo KR (λ ) 0.710 69 Å)
Mo KR (λ ) 0.710 69 Å)
ω-2θ
55
ω-2θ
50.0
3817
299
2586
307
no. of variables, p
R
Rw
0.028
0.033
0.36
0.021
0.031
0.60
largest peak in final diff map, e Å-3
P r ep a r a tion s of 3a -k by th e Secon d P r oced u r e. Prod-
ucts 3a -k were also prepared (using the same amounts of
corresponding starting materials) by a second procedure, which
is almost the same as the first procedure described above,
except without the air-bubbling step before the open-air TLC
separatron. The quantities and yields of 3a -k obtained by
the second procedure are as follows: 3a , 100 mg (17%); 3b,
115 mg (19%); 3c, 50 mg (8%); 3d , 170 mg (26%); 3e, 142 mg
(21); 3f, 100 mg (16%); 3g, 110 mg (16%); 3h , 130 mg (19%);
3i, 30 mg (4%); 3j, 40 mg (5%); 3k , 40 mg (6%).
refined anisotropically. Hydrogen atoms were included but
not refined. Final refinement by the full-matrix least-squares
method for non-hydrogen atoms converged to weighted and
unweighted agreement factors. All calculations were per-
formed on
a Micro-Vax II computer using the TEXSAN
program package. Details of crystal parameters, data collec-
tion, and structure refinement for 3d and 3k are given in Table
4.
Cr ystal Str u ctu r e Deter m in ation s of 3d an d 3k. Single-
crystals of 3d and 3k suitable for X-ray diffraction were grown
by slow evaporation of their CH2Cl2/petroleum ether solutions
in a refrigerator. A single crystal of 3d or 3k measuring
approximately 0.20 × 0.20 × 0.30 mm was mounted on a glass
fiber and placed in a Rigaku AFC7R diffractometer with
graphite-monochromated Mo-KR radiation and a 12 kW
rotating anode generator. All reflections (3095 reflections for
3d and 4047 for 3k ) were collected at 20 °C by the ω-2θ scan
mode, the independent reflections of which with I g 3σ(I) were
considered to be observed and used in subsequent refinements.
Data were corrected for Lp and absorption factors.
Ack n ow led gm en t. We are grateful to the National
Natural Science Foundation of China, the Laboratory
of Organometallic Chemistry, and the State Key Labo-
ratory of Structural Chemistry for financial support of
this work.
Su p p or tin g In for m a tion Ava ila ble: Full tables of crystal
data, atomic coordinates and thermal parameters, and bond
lengths and angles for 3d and 3k (18 pages). Ordering
information is given on any current masthead page.
The structures were solved by direct methods and expanded
using Fourier techniques. The non-hydrogen atoms were
OM980035W