Syntheses of new Mo(II) and W(II) mono(hydrosulfido) complexes and their conversion into di- and tetranuclear sulfido-bridged heterobimetallic complexes

Article abstract of DOI:10.1016/j.jorganchem.2009.07.032

Treatment of [Cp′MH(CO)₃] (M = Mo, W; Cp′ = η⁵-C₅H₅ (Cp), η⁵-C₅Me₅ (Cp*)) with 1/8 equiv of S₈ in THF, followed by the reaction with dppe under UV irradiation, gave ne

Full text of DOI:10.1016/j.jorganchem.2009.07.032

Journal of Organometallic Chemistry 694 (2009) 3775–3780
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Journal of Organometallic Chemistry
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Syntheses of new Mo(II) and W(II) mono(hydrosulfido) complexes and their
conversion into di- and tetranuclear sulfido-bridged heterobimetallic complexes
*
Kentaro Iwasa, Hidetake Seino, Yasushi Mizobe
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan
a r t i c l e i n f o
a b s t r a c t
Treatment of [Cp0MH(CO)3] (M = Mo, W; Cp0 =
followed by the reaction with dppe under UV irradiation, gave new mono(hydrosulfido) complexes
[Cp0M(SH)(CO)(dppe)] (Cp0 = Cp: M = Mo (5), W (6); Cp0 = Cp*: M = Mo (7), W (8); dppe = Ph2PCH2-
CH2PPh2). When 5 and 6 dissolved in THF were allowed to react with [RhCl(PPh3)3] in the presence of
g g
5-C5H5 (Cp), 5-C5Me5 (Cp*)) with 1/8 equiv of S8 in THF,
Article history:
Received 3 June 2009
Received in revised form 14 July 2009
Accepted 16 July 2009
Available online 27 July 2009
base, heterodinuclear complexes with bridging S and dppe ligands [CpM(CO)(l-S)-(l-dppe)Rh(PPh3)]
(M = Mo (9), W(10)) were obtained. Semi-bridging feature of the CO ligands were also demonstrated.
Upon standing in CH2Cl2 solutions, 9 and 10 were converted further to the dimerization products
Keywords:
Hydrosulfido complex
Sulfido complex
Molybdenum
[(CpM)2{Rh(dppe)}2(
clear 9 and tetranuclear 13 have been determined by the X-ray diffraction.
Ó 2009 Elsevier B.V. All rights reserved.
l2-CO)2(l3-S)2] (M = Mo (13), W). Detailed structures of mononuclear 7 and 8, dinu-
Tungsten
Mixed-metal sulfido complexes
1. Introduction
bimetallic complexes in this research group [3d,5] arises, at least
in part, from the relation of the sulfido-bridged groups 6 and 9 me-
tal complexes with the active sites of hydrodesulfurization cata-
lysts, although no intriguing reactivities towards organo-sulfur
compounds including thiophenes have been clarified yet for the
heterobimetallic complexes reported in this paper.
Sulfido-bridged multinuclear complexes are of much interest
because of their relation to the active sites of certain biological
and industrial catalysts [1]. Recent studies in this group have fo-
cused on the development of the rational methods to construct
the desired di- and polynuclear cores with bridging sulfur ligands
[2]. In the course of these studies, it has been shown by us and oth-
ers that the employment of bis(hydrosulfido) complexes contain-
2. Results and discussion
ing M(l-SH)2M or M(SH)2 centers are quite potential methods to
2.1. Preparation of new mono(hydrosulfido) complexes
prepare a variety of homo- and heterometallic complexes with
bridging sulfido ligands [2,3]. However, the complexes with only
one hydrosulfido ligand are less precedented and their transforma-
tions into the multimetallic sites bridged by only one sulfido ligand
have been investigated barely except for those derived from
When Mo and W mono(hydrosulfido) complexes [Cp0M(SH)-
(CO)3], which were generated in situ from hydrido-carbonyl com-
plexes [Cp0MH(CO)3] (Cp0 = Cp: M = Mo (1), W (2); Cp0 = Cp*:
M = Mo (3), W (4); Cp =
g g
5-C5H5; Cp* = 5-C5Me5) and S8 according
[Cp*IrH(SH)(PMe3)] (Cp* =
g
5-C5Me5) [4].
to the literature [6], were treated with dppe under UV irradiation
in THF at 0 °C, new mono(hydrosulfido) complexes [Cp0M(SH)
(CO)(dppe)] (Cp0 = Cp: M = Mo (5), W (6); Cp0 = Cp*: M = Mo (7),
W (8); dppe = Ph2PCH2CH2PPh2) were obtained by replacement of
two CO ligands with dppe (Scheme 1). Due to the instability of
[Cp0M(SH)(CO)3], preparation of 5–8 by thermal substitution at
higher temperatures without UV irradiation was unsuccessful.
Complexes 5–8 were characterized by spectroscopic and analytical
data. For 7 and 8, an X-ray analysis was also undertaken.
Now we have found that the Mo(II) and W(II) mono(hydrosulf-
ido) complexes newly prepared in this study can serve as precur-
sors to heterodinuclear complexes having the Mo–Rh and W–Rh
cores bridged by only one sulfide together with one dppe ligand.
Interestingly, successive dimerization reactions converting these
dinuclear complexes into sulfido-bridged tetranuclear clusters
have also been observed. In this paper, we wish to describe the de-
tails of these reactions, demonstrating the new route to sulfido-
bridged multinuclear complexes starting from mono(hydrosulfido)
complexes. Choice of group 9 metals as the counter part in the
In the IR spectra, the weak bands characteristic to
2528, 2530, and 2512 cmꢀ1 together with the strong
at 1829, 1810, 1821, and 1814 cmꢀ1 were observed for 5, 6, 7,
and 8, respectively. It is noteworthy that the (CO) value of
1829 cmꢀ1 observed for 5, viz. [CpMo(SH)(CO)(dppe)], is
m
(SH) at 2542,
m
(CO) bands
m
* Corresponding author. Fax: +81 3 5452 6361.
E-mail address: ymizobe@iis.u-tokyo.ac.jp (Y. Mizobe).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.07.032

3776
K. Iwasa et al. / Journal of Organometallic Chemistry 694 (2009) 3775–3780
Cp'
Cp'
M
Cp'
M
S
8
dppe
M
HS
P
H
C
HS
hν
C
O
C
O
P
O
C
C
C
C
O
O
O
O
P = PPh
2
1: Cp' = Cp, M = Mo
2: Cp' = Cp, M = W
3: Cp' = Cp*, M = Mo
4: Cp' = Cp*, M = W
5: Cp' = Cp, M = Mo
6: Cp' = Cp, M = W
7: Cp' = Cp*, M = Mo
8: Cp' = Cp*, M = W
Scheme 1.
somewhat lower than those of the Cl and H analogues, [CpMoCl-
(CO)(dppe)] (1845 cmꢀ1) [7] and [CpMoH(CO)(dppe)] (1840 cmꢀ1
)
[8]. The 1H NMR spectra exhibited the high-field resonances
assignable to SH protons coupled to two inequivalent P atoms (5:
ꢀ3.17; 6: ꢀ2.41; 7: ꢀ2.17; 8: ꢀ1.62 ppm). The 31P{1H} NMR spec-
tra displayed two signals due to these P atoms of dppe ligands,
where the JP–P values are much larger for Mo complexes 5
(35 Hz) and 7 (31 Hz) than for W complexes 6 (6 Hz) and 8
(unobservable).
The structures of 5–8 have been confirmed by the single-crystal
X-ray analysis for 7 and 8. Selected bond distances and angles in 7
and 8 are listed in Table 1, while the ORTEP drawing for 7, which is
essentially identical with that of 8, is depicted in Fig. 1.
Fig. 1. An ORTEP drawing for 7 (30% probability level). Hydrogen atoms are omitted
for clarity.
S
t
Ph P
3
Cp
[RhCl(PPh ) ] / NEt or KOBu
3 3
3
M
M'
5 or 6
C
t
or [IrCl(coe) ] / PPh / KOBu
P
2 2
3
P
O
Complex 7 has an expected four-legged piano-stool structure,
although it is distorted considerably. Thus, with respect to the
pseudo-trans bond angles around the metal centers, the S(1)–M–
P(1) angles at 136.84(2)° for 7 (M = Mo) and 137.05(5)° for 8
(M = W) are much larger than the P(2)–M–C(11) angles at
105.25(7)° in 7 and 106.1(2)° in 8. Analogous distortion was ob-
served previously for the related complexes [Cp*W(SH)(CO)3] [9]
and [CpMoBr(CO)(dppe)] [10], where the pseudo-trans bond angles
associated with the SH and Br ligands are significantly larger:
S–W–C (trans) at 134.9(4)° versus C–W–C (trans) at 108.2(2)° in
the former and Br–Mo–P (trans) at 143.07(3)° versus P–Mo–C
(trans) at 113.3(2)° in the latter.
9: M = Mo, M' = Rh
10: M = W, M' = Rh
11: M = Mo, M' = Ir
12: M = W, M' = Ir
Scheme 2.
yielding the untractable products. The structure of 9 has been
determined in detail by the X-ray analysis, while the preliminary
X-ray results have confirmed the structure of 10 essentially identi-
cal with that of 9.
The ORTEP drawing for 9 is shown in Fig. 2, while important
interatomic distances and angles therein are listed in Table 2. Com-
plex 9 has a dinuclear core bridged by one sulfide and one dppe.
The CO molecule also bridges the Mo–Rh bond but the interaction
with Rh is weak. Thus, the Mo–C(6) bond distance and the
Mo–C(6)–O angle are 1.969(6) Å and 151.6(4)°, whereas the Rh–
C(6) bond length and Rh–C(6)–O angle are 2.202(4) Å and
126.5(4)°. Such semi-bridging mode of CO bound to Mo–Rh core
2.2. Preparation of sulfido-bridged dinuclear heterometallic complexes
from 5 and 6
Reaction of 5 with [RhCl(PPh3)3] in THF in the presence of
excess NEt3 afforded the heterobimetallic complex [CpMo(CO)
(
l
-S)(
l
-dppe)Rh(PPh3)] (9) having one sulfide and one dppe as
ligands. The analogue [CpW(CO)( -S)(
bridging
W
l
l-
dppe)Rh(PPh3)] (10) was obtained from 6 but by the use of the
stronger base KOBut in place of NEt3 (Scheme 2). Reaction of 5
and [RhCl(PPh3)3] in the presence of KOBut did not proceed cleanly,
Table 1
Selected interatomic distances (Å) and angles (°) in 7 and 8.
7 (M = Mo)
8 (M = W)
M(1)–S(1)
M(1)–P(1)
M(1)–P(2)
M(1)–C(11)
C(11)–O(1)
2.5355(7)
2.4913(6)
2.4758(6)
1.924(2)
1.169(3)
2.511(2)
2.468(2)
2.467(1)
1.927(5)
1.166(7)
S(1)–M(1)–P(1)
S(1)–M(1)–P(2)
S(1)–M(1)–C(11)
P(1)–M(1)–P(2)
P(1)–M(1)–C(11)
P(2)–M(1)–C(11)
M(1)–C(11)–O(1)
136.84(2)
74.26(2)
79.70(7)
76.07(2)
78.70(6)
105.25(7)
173.3(2)
137.05(5)
77.55(4)
79.2(2)
76.09(4)
76.4(2)
106.1(2)
174.6(5)
Fig. 2. An ORTEP drawing for 9 (30% probability level). Hydrogen atoms are omitted
for clarity.

K. Iwasa et al. / Journal of Organometallic Chemistry 694 (2009) 3775–3780
3777
Table 2
Selected interatomic distances (Å) and angles (°) in 9.
2.3. Formation of tetranuclear clusters from 9 and 10
When the CH2Cl2 solutions of 9 and 10 were left standing at
room temperature for a week, sulfido-bridged tetranuclear clusters
[(CpM)2{Rh(dppe)}2(l3-S)2(l2-CO)2] (M = Mo (13), W (14)) precip-
itated as purple crystals in low yields (Scheme 3). Dimerization
probably took place owing, at least in part, to the electron-deficient
nature of 9 and 10, which favors the transformation of the core
structure into that with more metal–metal interactions. Clusters
13 and 14 are practically insoluble to common solvents and have
been characterized by the X-ray analysis of 13. Pertinent inter-
atomic parameters are listed in Table 3.
Mo(1)–Rh(1)
Mo(1)–P(1)
Rh(1)–S(1)
Rh(1)–P(3)
C(6)–O(1)
2.7361(7)
2.4515(15)
2.2916(17)
2.2911(12)
1.200(7)
Mo(1)–S(1)
Mo(1)–C(6)
Rh(1)–P(2)
Rh(1)–C(6)
2.2599(12)
1.969(6)
2.2540(15)
2.202(4)
Mo(1)–S(1)–Rh(1)
Mo(1)–C(6)–O(1)
S(1)–Mo(1)–P(1)
P(1)–Mo(1)–C(6)
S(1)–Rh(1)–P(3)
P(2)–Rh(1)–P(3)
P(3)–Rh(1)–C(6)
73.90(4)
151.6(4)
114.68(5)
81.5 (2)
88.95(5)
100.85(5)
145.4(1)
Mo(1)–C(6)–Rh(1)
Rh(1)–C(6)–O(1)
S(1)–Mo(1)–C(6)
S(1)–Rh(1)–P(2)
S(1)–Rh(1)–C(6)
P(2)–Rh(1)–C(6)
81.79(18)
126.5(4)
99.4(1)
163.32(5)
91.9(2)
87.7(2)
As shown in Fig. 3, 13 has a crystallographic inversion center at
the midpoint of the raft-type tetranuclear Mo2Rh2 core with two
was
demonstrated
previously
for
e.g.,
[{Cp*Rh(S2C2
l3-S ligands each bridging two Mo and one Rh atoms. As expected
(B10H10))}2M(CO)2] (M = Mo [11], W [12]), where the Rh–CO dis-
tances are significantly longer (2.49–2.58 Å) than those in 9. If
the Mo–Rh bond is ignored, the geometry around Mo is a distorted
three-legged piano-stool and that around Rh is a distorted T-shape
with further weak interaction with CO. Around Rh, the Mo atom is
almost coplanar with the Rh–P(2)–P(3) plane with the distance of
0.03 Å, while the separations of S(1) and C(6) from this plane are
0.54 and 1.22 Å, respectively, and the Rh–P(2)–P(3) and Rh–S(1)–
C(6) planes are oriented with the dihedral angle of 36.6°. It is note-
worthy that the Mo–Rh distance at 2.7361(7) Å is shorter than
those of the sulfido-bridged Mo–Rh complexes reported previ-
ously. Thus, for nine Mo–Rh complexes with sulfido bridge(s)
found by the SciFinder Scholar search, the precedented sulfido-
bridged Mo–Rh distances are in the range 2.83–3.12 Å [3b,13],
where the shortest distance at 2.833(1) Å was observed in the tri-
from the electron count of only 60 for the formal Mo(II)2Rh(I)2
core, metal–metal single-bonds exist between two Mo atoms sep-
arated by 2.741(2) Å and at the two Mo–Rh edges with the distance
at 2.772(2) Å. With respect to the remaining two Mo–Rh edges, the
distance at 3.020(2) Å also suggests the presence of weak bonding
interactions. The shorter Mo–Rh edges are each bridged further by
CO almost symmetrically (see Table 3). Consistently, the IR spec-
trum of 13 shows strong
acteristic to the symmetrically bridging CO ligand. Cluster 14
m
(CO) band at 1676 cmꢀ1, which is char-
shows essentially the same IR spectrum, in which the m(CO) band
is observed at 1656 cmꢀ1. Ignoring the metal–metal interactions,
the Mo center has a three-legged piano-stool structure, while the
geometry around Rh is square planar. The S–Rh–C(6)–Mo torsion
angle at almost 180° indicates that these four atoms are essentially
coplanar.
nuclear cluster [{Mo(S2CNEt2)}2(l2-Cl){Rh(PMe2Ph)2}(l3-S)(l2
-
Dissociation of PPh3 from Rh site, followed by the migration of
S)3] [14]. Short Mo–Rh bond lengths in 9 presumably results from
the electron-deficient nature of its dinuclear core with only 30-
electron count.
one P atom of l-dppe from Mo or W to Rh, might result in the
dimerization of these species at the coordinatively unsaturated
Mo or W site with potentially face-bridging S ligand, yielding 13
and 14. Closely related core structures have been demonstrated
previously, e.g. for the Mo2Fe2 cluster [(Cp00Mo)2{Fe(CO)3}2
In the IR spectra of 9 and 10, the m(SH) bands of 5 and 6 disap-
peared. The strong
m(CO) bands were observed at 1971 and
1970 cmꢀ1 for 9 and 10, which are shifted to higher frequency re-
(
l
3-S)2(
l
2-CO)2] (Cp00 = Cp (15),
g
5-C5H4Me) [16] and Mo4 cluster
5-C5H4COOR: R = Me, Et)
gion by ca. 140 cmꢀ1 from those of 5 and 6. Change in the binding
[(Cp°Mo)2Mo2(
l
3-S)2( 2-CO)4] (Cp° = g
l
site of the CO ligands from the strongly
p
-back donating, 18-elec-
[17]. However, synthesis of such clusters via the dimerization of
well-defined heterobimetallic core is not precedented. It is also
noteworthy that in a 62-electron cluster 15 all of the Mo–Mo,
tron Mo and W centers with the chelating dppe ligand in 5 and 6 to
the 16-electron Mo and W centers with only one coordinated P
atom in 9 and 10 might result in the high-frequency shifts of
two Mo–Fe (with
l-CO), and two Mo–Fe (without l-CO) bonds
m
(CO) bands, even though they are adopting semi-bridging mode.
at 2.821(1), 2.776(1), and 2.805(1) Å, respectively, fall in the range
of metal–metal single bond to provide the electron-precise core. In
contrast, a 60-electron 13 somehow has only three single-bonds
together with two much weaker bonds in spite of the less electron
count.
The 1H NMR spectra show the Cp resonances as doublets of dou-
blets, while the 31P{1H} NMR spectra exhibit three signals each
coupled with other two P and one Rh atoms. These spectral data
for 9 and 10 are consistent with their X-ray structures.
Although syntheses of the Ir analogues by using [IrCl(PPh3)3] as
the Ir source were unsuccessful, treatment of 5 and 6 with a mix-
ture of 0.5 equiv of [IrCl(coe)2]2 (coe = cyclooctene) and one equiv
3. Experimental
of PPh3 afforded [CpM(CO)(l-S)(l-dppe)Ir(PPh3)] (11: M = Mo,
3.1. General considerations
12: M = W) in low yields (Scheme 2). However, since analytically
pure crystals were not available, both 11 and 12 were character-
ized only spectroscopically. In the reaction mixtures of 7 and 8
with [RhCl(PPh3)3] or [IrCl(coe)2]2/PPh3 conducted under analo-
All manipulations were carried out under N2 using standard
Schlenk techniques. Solvents were dried by common methods
gous conditions, formations of [Cp*M(CO)(l-S)(l
-dppe)M0(PPh3)]
O
Cp
(M = Mo, W; M0 = Rh, Ir) were shown by their NMR spectra.
However, due to the high solubilities of these Cp* analogues into
THF, we could not obtain these products as crystals or solid by
the procedure analogous to that to isolate the Cp complexes such
as 9 and 10. Attempts to isolate Cp* analogues by crystallization
from other solvents resulted in decomposition of the products.
Complexes 9–12 are the rare examples of the dinuclear
complexes having both sulfido and dppe bridges, although such
fragments were observed as the partial cores in certain sulfido
clusters [15].
C
S
P
P
M
9 or 10
Rh
Rh
CH Cl
2
2
M
P
S
P
C
Cp
O
13: M = Mo
14: M = W
Scheme 3.

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K. Iwasa et al. / Journal of Organometallic Chemistry 694 (2009) 3775–3780
Table 3
PCH2), 1.9 (m, 1H, PCH2), ꢀ3.17 (dd, JP–H = 8.8, 0.8 Hz, 1H, SH).
31P{1H} NMR (CDCl3): d 89.6, 71.5 (d, JP–P = 35 Hz, 1P each). Anal.
Calc. for C38H36OMoP2S: C, 65.33; H, 5.19. Found: C, 65.06; H,
5.27%.
Selected interatomic distances (Å) and angles (°) in 13.
Mo(1)–Mo(1*)
Mo(1)–Rh(1*)
Mo(1)–S(1)
Rh(1)–S(1)
Rh(1)–P(2)
Rh(1)–C(6)
2.741(2)
3.020 (2)
2.324(4)
2.308(3)
2.309(4)
2.05(2)
Mo(1)–Rh(1)
Rh(1)ꢁꢁꢁRh(1*)
Mo(1)–S(1*)
Rh(1)–P(1)
2.772(2)
5.108(2)
2.378(4)
2.251(3)
2.05(2)
3.3. Preparation of 6
Mo(1)–C(6)
This complex was prepared similarly from
3.00 mmol), S8 (96 mg, 0.37 mmol), and dppe (1.31 g, 3.30 mmol)
under irradiation for 12 h, and isolated as an yellow–orange pow-
2
(1.00 g,
Mo(1*)–Mo(1)–Rh(1)
Mo(1*)–Mo(1)–Rh(1*)
Mo(1)–S(1)–Rh(1)
Mo(1)–C(6)–Rh(1)
Rh(1)–C(6)–O(1)
S(1)–Rh(1)–P(1)
66.42(4)
57.28(4)
73.5(1)
85.3(6)
136(1)
173.3(2)
100.8(4)
85.2(4)
Mo(1)–Rh(1)–Mo(1*)
Mo(1)–S(1)–Mo(1*)
Mo(1*)–S(1)–Rh(1)
Mo(1)–C(6)–O(1)
S(1)–Mo(1)–S(1*)
S(1)–Rh(1)–P(2)
56.30(4)
71.3(1)
80.2(1)
138(1)
108.7(2)
90.5(2)
84.0(2)
165.2(4)
der of 6ꢁC6H6 (1.05 g, 44% yield). IR (KBr): 2528w
m(SH);
1810vs cmꢀ1 (CO). 1H NMR (CDCl3): d 7.7–7.2 (m, 26H, Ph and
m
S(1)–Rh(1)–C(6)
P(1)–Rh(1)–C(6)
P(1)–Rh(1)–P(2)
P(2)–Rh(1)–C(6)
C6H6), 4.56 (d, JP–H = 2.4 Hz, 5H, Cp), 2.6–2.3 (m, 3H, PCH2), 2.0
(m, 1H, PCH2), ꢀ2.41 (dd, JP–H = 9.0, 1.4 Hz, 1H, SH). 31P{1H} NMR
(CDCl3): d 60.3 (d with 183W satellites, JP–P = 6 Hz, JP–W = 245 Hz,
1P), 47.3 (d with 183W satellites, JP–P = 6 Hz, JP–W = 303 Hz, 1P).
Anal. Calc. for C38H36OP2SW: C, 58.03; H, 4.61. Found: C, 58.24;
H, 4.71%.
and distilled under N2 before use. Complexes 1, 2 [18], 3 [19], 4
[20], [RhCl(PPh3)3] [21], and [IrCl(coe)2]2 [22] were prepared
according to the literature methods, while the chemicals were ob-
tained commercially and used as received except for NEt3, which
was dried over KOH and distilled under N2 before use. UV irradia-
tion was conducted by the use of a Ushio Optical Module X mer-
cury lamp (250 W).
IR spectra were recorded on a JASCO FT/IR-420 spectrometer,
while 1H and 31P{1H} NMR spectra were obtained from a JEOL al-
pha-400 spectrometer. Elemental analyses were done with a Per-
kin–Elmer 2400 series II CHN analyzer.
3.4. Preparation of 7
The reaction mixture was obtained similarly from 3 (171 mg,
0.54 mmol), S8 (18 mg, 0.069 mmol), and dppe (237 mg,
0.60 mmol) under UV irradiation for 16 h, which was dried up
and the residue was stirred with ether (5 mL) to give orange slurry.
This mixture was filtered off and the solid was extracted with THF.
Addition of ether to the concentrated extract afforded 7ꢁ0.5Et2O as
red crystals (61 mg, 16% yield). IR (KBr): 2530w
m(SH);
1821vs cmꢀ1 (CO). 1H NMR (C6D6): d 7.8–7.6 (m, 6H, Ph), 7.37
m
3.2. Preparation of 5
(m, 2H, Ph), 7.2–6.9 (m, 12H, Ph), 3.26 (q, 2H, OCH2CH3), 2.2 (m,
1H, PCH2), 2.0–1.8 (m, 3H, PCH2), 1.47 (s, 15H, Cp*), 1.11 (t, 3H,
OCH2CH3), ꢀ2.17 (dd, JP–H = 6.2, 1.4 Hz, 1H, SH). 31P{1H} NMR
(C6D6): d 89.5, 65.8 (d, JP–P = 31 Hz, 1P each). Anal. Calc. for
C39H45O1.5MoP2S: C, 64.37; H, 6.23. Found: C, 64.37; H, 6.16%.
Elemental sulfur (S8, 291 mg, 1.13 mmol) was added into a THF
solution (60 mL) of 1 (2.25 g, 9.13 mmol) cooled to ꢀ5 °C, and the
mixture was stirred for 1.5 h at this temperature in the dark. After
adding dppe (3.99 g, 10.0 mmol), the mixture was subjected to UV
irradiation at 0 °C with stirring. Monitoring the reaction by 1H NMR
spectroscopy indicated that it took ca. 32 h until the reaction com-
pleted. The resultant mixture was dried up in vacuo and the resi-
due was stirred with benzene (20 mL) to give yellow suspension,
which was filtered off. The yellow powder of 5ꢁC6H6 was washed
with benzene (20 mL ꢂ 4) and dried (3.74 g, 59% yield). IR (KBr):
3.5. Preparation of 8
Complex 8 was prepared from 4 (819 mg, 2.03 mmol) by the
same method as that for 7, S8 (65 mg, 0.25 mmol), and dppe
(889 mg, 2.23 mmol), and isolated as orange crystals (376 mg,
2542w
m
(SH); 1829vs cmꢀ1
m
(CO). 1H NMR (CDCl3): d 7.7–7.2 (m,
24% yield). IR (KBr): 2512w
(C6D6): 7.8–7.6 (m, 6H, Ph), 7.4–7.3 (m, 2H Ph), 7.2–6.9
m m
(SH); 1824vs cmꢀ1 (CO). 1H NMR
26H, Ph and C6H6), 4.48 (d, JP–H = 2.4 Hz, 5H, Cp), 2.6–2.3 (m, 3H,
d
Fig. 3. An ORTEP drawing for 13 (50% probability level). Hydrogen atoms are omitted for clarity.

K. Iwasa et al. / Journal of Organometallic Chemistry 694 (2009) 3775–3780
3779
(m, 12H, Ph), 2.2 (m, 1H, PCH2), 2.1–1.7 (m, 3H, PCH2), 1.52 (s, 15H,
Cp*), ꢀ1.62 (dd, JP–H = 7.2, 2.0 Hz, 1H, SH). 31P{1H} NMR (C6D6): d
58.0 (s with 183W satellites, JP–W = 257 Hz, 1P), 43.1 (s with 183W
satellites, JP–W = 288 Hz, 1P). Anal. Calc. for C37H40OP2SW: C,
57.08; H, 5.18. Found: C, 57.14; H, 5.19%.
2H each, Ph), 5.09 (dd, JP–H = 2.2, 0.6 Hz, 5H, Cp), 3.45, 3.19, 2.54,
1.77 (m, 1H each, PCH2). 31P{1H} NMR (CD2Cl2): d 37.6 (dd with
183W satellites, JP–P = 15, 4 , JP–W = 380 Hz, 1P, W–dppe), 34.4 (dd,
JP–P = 21, 15 Hz, 1P, Ir–P), 13.7 (dd, JP–P = 21, 4 Hz, 1P, Ir–P). Purifi-
cation of 12 was also unsuccessful due to its instability in
solutions.
3.6. Preparation of 9
3.10. Preparation of 13
Into
0.499 mmol) cooled to ꢀ78 °C were added 5 (349 mg, 0.499 mmol)
and NEt3 (140 L, 1.00 mmol) with stirring. The mixture was
a THF solution (50 mL) of [RhCl(PPh3)3] (462 mg,
Upon standing
a CH2Cl2 solution (3 mL) of 9 (32 mg,
l
0.032 mmol) at room temperature, purple crystals of 13ꢁ2CH2Cl2
warmed gradually to room temperature and stirred continuously
at that temperature for 2 days. The resultant solution was concen-
trated to ca. 10 mL and ether (50 mL) was added. After filtration,
the filtrate was kept in the fridge (ꢀ20 °C) to give 9 slowly as the
precipitated, the yield of which was 10 mg (39%) after a week. IR
(KBr): 1676s cmꢀ1
m(CO). Anal. Calc. for C66H62O2P4S2Cl4Mo2Rh2:
C, 49.01; H, 3.87. Found: C, 48.58; H, 3.71%. Due to the quite poor
solubility to the common solvents, NMR spectra could not be
recorded.
black crystals (370 mg, 75% yield). IR (KBr): 1971s cmꢀ1 (CO). 1H
m
NMR (CD2Cl2): d 7.59 (m, 2H, Ph), 7.4–7.05 (m, 28H Ph), 6.94 (m,
1H, Ph), 6.74, 6.62 (m, 2H each, Ph), 4.99 (dd, JP–H = 1.6, 0.6 Hz,
5H, Cp), 3.29, 3.06, 2.47, 1.86 (m, 1H each, PCH2). 31P{1H} NMR
(CD2Cl2): d 62.6 (ddd, JP–P = 16, 6 Hz, JP–Rh = 3 Hz, 1P, Mo–dppe),
46.5 (ddd, JP–P = 43, 16 Hz, JP–Rh = 177 Hz, 1P, Rh–P), 31.9 (ddd,
JP–P = 43, 6 Hz, JP–Rh = 187 Hz, 1P, Rh–P); Assignment of two latter
P signals to either Rh–dppe or Rh–PPh3 is uncertain. Anal. Calc.
for C50H44OP3SRhMo: C, 60.99; H, 4.50. Found: C, 60.54; H, 4.76%.
3.11. Preparation of 14
Similar procedure using 10 (33 mg, 0.031 mmol) gave
14ꢁ2CH2Cl2 as purple crystals (4.1 mg, 16% yield). IR (KBr): 1656s
cmꢀ1
m(CO). The IR spectrum is totally in good agreement with that
of 13 except for the shift of the m
(CO) band by 20 cmꢀ1. Anal. Calc.
for C66H62O2P4S2Cl4W2Rh2: C, 44.27; H, 3.49. Found: C, 43.91; H,
3.71%. Due to the quite poor solubility to the common solvents,
NMR spectra could not be recorded.
3.7. Preparation of 10
This complex was prepared similarly from [RhCl(PPh3)3]
(185 mg, 0.200 mmol) and 6 (157 mg, 0.200 mmol) by using KOBut
(34 mg, 0.30 mmol) in place of NEt3. The yield of 10 as black crys-
3.12. X-ray crystallography
tals was 147 mg (69%). IR (KBr): 1970s cmꢀ1
m
(CO). 1H NMR
Single crystals of 7ꢁ0.5Et2O, 8, 9ꢁTHFꢁ0.5Et2O, and
10ꢁTHFꢁ0.5Et2O were sealed in glass capillaries under argon, while
that of 13ꢁ2CH2Cl2 was mounted on a cryoloop with paratone oil.
Diffraction studies were done by a Rigaku Mercury-CCD diffrac-
(CD2Cl2): d 7.73 (m, 2H, Ph), 7.5–7.2 (m, 28H Ph), 6.90 (m, 1H,
Ph), 6.66, 6.58 (m, 2H each, Ph), 5.08 (dd, JP–H = 1.6, 0.4 Hz, 5H,
Cp), 3.48, 3.14, 2.66, 1.93 (m, 1H each, PCH2). 31P{1H} NMR
(CD2Cl2): d 50.4 (ddd, JP–P = 42, 5 Hz, JP–Rh = 193 Hz, 1P, Rh–P),
33.7 (ddd, JP–P = 42, 15 Hz, JP–Rh = 172 Hz, 1P, Rh–P), 33.3 (ddd with
183W satellites, JP–P = 15, 5 Hz, JP–Rh = 2 Hz, JP–W = 376 Hz, 1P,
W–dppe). Assignment of two former P signals to either Rh–dppe
or Rh–PPh3 is uncertain. Anal. Calc. for C50H44OP3SRhMo: C,
55.99; H, 4.14. Found: C, 55.85; H, 4.41%.
tometer equipped with
a graphite-monochromatized Mo Ka
source at 20 °C for 7, 8, 9, and 10 and at ꢀ160 °C for 13. Details
are summarized in Table 4. Data collections were performed by
using the CRYSTALCLEAR program package [23]. All data were corrected
for Lorentz and polarization effects as well as absorption.
Structure solution and refinements were conducted by using
the CRYSTALSTRUCTURE program package [24]. The positions of non-
hydrogen atoms were determined by Patterson methods (PATTY
[25]) and subsequent Fourier synthesis (DIRDIF99 [26]), which were
refined anisotropically by full-matrix least-squares techniques.
Hydrogen atoms except for those attached to the disordered atoms
were placed at the calculated positions and included at the final
stages of the refinements with fixed parameters. For 7 and 8, the
SH hydrogens were unable to be located and not included in the
refinements of their structures. For 13, due to the unsatisfactory
quality of the data, all C atoms were refined isotropically.
3.8. Preparation of 11
Into a THF solution (40 mL) of [IrCl(coe)2]2 (90 mg, 0.10 mmol)
was added PPh3 (53 mg, 0.20 mmol). The mixture was stired at
room temperature for 30 min and then cooled to ꢀ78 °C. After
addition of 5 (140 mg, 0.201 mmol) and KOBut (34 mg, 0.30 mmol),
the mixture was warmed gradually to room temperature with stir-
ring. The resultant solution was concentrated to ca. 2 mL and ether
(20 mL) was added with stirring. After filtration, the filtrate was
kept at ꢀ78 °C to give 11 as black crystals (17 mg). IR (KBr):
Preliminary X-ray data for 10ꢁTHFꢁ0.5Et2O: formula,
C56H54.50O2.50P3SRhW; Fw = 1179.28; space group, P21/a (no. 14);
a = 11.395(5) Å, b = 34.50(1) Å, c = 13.779(6) Å, b = 111.962(2)°,
1959s cmꢀ1 (CO). 1H NMR (CD2Cl2): d 7.7–7.0 (m, 30H, Ph), 6.99
m
(m, 1H, Ph), 6.73, 6.63 (m, 2H each, Ph), 5.01 (dd, JP–H = 1.6,
0.4 Hz, 5H, Cp), 3.30, 3.16, 2.37, 1.70 (m, 1H each, PCH2). 31P{1H}
NMR (CD2Cl2): d 70.1 (dd, JP–P = 17, 3 Hz, 1P, Mo-dppe), 33.4 (dd,
JP–P = 21, 17 Hz, 1P, Ir–P), 12.7 (dd, JP–P = 21, 3 Hz, 1P, Ir–P). Analyt-
ically pure 11 was not available, since it gradually decomposed
when redissolved in solvents for recrystallization.
V = 5023(4) Å3;
Z = 4;
q
calc = 1.559 g cmꢀ1
;
crystal
size,
0.10 ꢂ 0.10 ꢂ 0.10 mm3; no. of unique reflections, 11 358; no. of
variables, 603; R1 value with I > 2r(I) and wR2 value with all data,
0.0386 and 0.187; GOF, 1.066.
3.9. Preparation of 12
4. Supplementary material
This complex was obtained from 6 (79 mg, 0.10 mmol), [IrCl
(coe)2]2 (45 mg, 0.050 mmol), PPh3 (27 mg, 0.10 mmol), and KOBut
(18 mg, 0.16 mmol) as black crystals (22 mg) by the same proce-
CCDC 739958, 739959, 739960, and 739961 contain the supple-
mentary crystallographic data for 7, 8, 9, and 13, respectively.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
dure as described above. IR (KBr): 1959s cmꢀ1
m
(CO). 1H NMR
(CD2Cl2): d 7.7–7.0 (m, 30H, Ph), 6.89 (m, 1H, Ph), 6.64, 6.58 (m,

3780
K. Iwasa et al. / Journal of Organometallic Chemistry 694 (2009) 3775–3780
Table 4
Crystal data for 7ꢁ0.5Et2O, 8, 9ꢁTHFꢁ0.5Et2O, and 13ꢁ2CH2Cl2.
7ꢁ0.5Et2O
8
9ꢁTHFꢁ0.5Et2O
13ꢁ2CH2Cl2
Formula
Fw
Crystal system
Space group
a (Å)
C39H45O1.50P2SMo
727.73
C37H40OP2SW
778.58
C56H57O2.50P3SMoRh
1093.89
C66H62O2P4S2Cl4Mo2Rh2
1614.73
Tetragonal
I41/a (no. 88)
31.517(4)
–
12.609(2)
90
12 525(3)
8
Monoclinic
P21/a (no. 14)
17.415(1)
11.2257(5)
18.484(1)
90.547(1)
3613.3(3)
4
Monoclinic
P21/a (no. 14)
17.156(4)
11.002(3)
18.956(5)
109.9291(9)
3364(2)
Monoclinic
P21/a (no. 14)
11.414(2)
34.586(6)
13.793(3)
111.9698(5)
5050(2)
b (Å)
c (Å)
b (°)
V (Å3-
Z
4
4
qcalc (g cmꢀ3)
Crystal size (mm3)
1.338
1.537
1.439
1.713
0.50 ꢂ 0.50 ꢂ 0.50
0.50 ꢂ 0.20 ꢂ 0.10
0.20 ꢂ 0.10 ꢂ 0.10
0.10 ꢂ 0.05 ꢂ 0.05
l
(cmꢀ1
)
5.39
36.23
7.523
12.92
2h minimum, maximum (°)
6, 55
6, 55
6, 55
6, 44
Unique reflections
Data of I > 2r(I)
8169 (Rint = 0.023)
6559
7537 (Rint = 0.047)
5536
11 540 (Rint = 0.054)
4880
3818 (Rint = 0.248)
1271
Variables
470
418
624
236
Transmission factor
0.555–0.764
0.033
0.103
0.308–0.696
0.0374
0.122
0.699–0.928
0.0388
0.1475
0.728–0.937
0.0564
0.1977
a
R1
wR2
b
Goodness-of-fit (GOF)c
1.036
1.041
1.027
1.024
P
P
a
b
c
R1
=
||F0|ꢀ|Fc||/ |F0| (I > 2
r
I).
P
P
wR2 = [ (w(F2o ꢀ Fc2)2)/ w(F2o)2]1/2 (all data).
GOF = [
R
w(|F0|ꢀ|Fc|)2]/{(no. observed)ꢀ(no. variables)}]1/2
.
[13] (a) K. Arashiba, S. Matsukawa, S. Kuwata, Y. Tanabe, M. Iwasaki, Y. Ishii,
Organometallics 25 (2006) 560;
Acknowledgement
(b) T. Fujimura, H. Seino, M. Hidai, Y. Mizobe, Inorg. Chim. Acta 358 (2005)
2449;
(c) H. Seino, T. Masumori, M. Hidai, Y. Mizobe, Organometallics 22 (2003)
3424;
This work was supported by Grant-in-Aid for Scientific Re-
search on Priority Areas (No. 18065005, ‘‘Chemistry of Concerto
Catalysis”) from the Ministry of Education, Culture, Sports, Science
and Technology, Japan.
(d) T. Ikada, S. Kuwata, Y. Mizobe, M. Hidai, Inorg. Chem. 38 (1999) 64;
(e) H. Akashi, K. Isobe, T. Shibahara, Inorg. Chem. 44 (2005) 3494;
(f) K. Herbst, M. Monari, M. Brorson, Inorg. Chem. 40 (2001) 2979.
[14] T. Ikada, Y. Mizobe, M. Hidai, Organometallics 20 (2001) 4441.
[15] (a) Q.-L. Wang, S.-N. Chen, X. Wang, G.-M. Wu, W.-H. Sun, H.-Q. Wang, S.-H.
Yang, Polyhedron 15 (1996) 2613;
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