Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine co-ligand and its transformation into MoRh2 and MoIr2 mixed-metal sulfido clusters

Article abstract of DOI:10.1039/b902386k

The treatment of a Mo(0) complex with a tetraphosphine co-ligand [Mo(κ⁴-P4)(Ph₂PCH₂CH₂PPh ₂)] (P4 = meso-o-C₆H₄(PPhCH₂CH ₂PPh₂)₂) with

Full text of DOI:10.1039/b902386k

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www.rsc.org/dalton | Dalton Transactions
Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine
co-ligand and its transformation into MoRh2 and MoIr2 mixed-metal
sulfido clusters†
Kentaro Iwasa, Hidetake Seino, Fumiya Niikura and Yasushi Mizobe*
Received 4th February 2009, Accepted 1st May 2009
First published as an Advance Article on the web 4th June 2009
DOI: 10.1039/b902386k
4
The treatment of a Mo(0) complex with a tetraphosphine co-ligand [Mo(k -P4)(Ph2PCH2CH2PPh2)]
(P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with H2S gas in toluene at room temperature afforded
4
[Mo(SH)2(k -P4)] (1), which demonstrates the first Mo(II) bis(hydrosulfido) complex. Its
trigonal-prismatic structure rarely observed for Mo(II) complexes has been determined by X-ray
analysis. The reactions of 1 with [RhCl(CO)2]2 and [IrCl(CO)2(p-toluidine)] in the presence of NEt3
4
resulted in the formation of the sulfido-bridged trinuclear clusters [Mo(k -P4)(m3-S)2{Rh(CO)2}2] (4)
4
and [Mo(k -P4)(m3-S)2{Ir(CO)2}2] (5), respectively. The X-ray diffraction study has disclosed that the
MoRh2 cluster 4 in the solid state exists in two isomeric forms arising from the different orientation of
P4 to the trigonal-prismatic Mo center, whereas the crystals of the Ir analogue 5 contains the molecules
corresponding to only one of the two isomers observed for 4. The fluxional features of 1, 4, and 5 in
solution have been confirmed by VT NMR studies.
◦
˚
Table 1 Selected bond distances (A) and angles ( ) in 1
Introduction
Hydrosulfido complexes are attracting much attention because
of their relevance to the active sites of commercial hydrodesul-
furization catalysts as well as certain metalloenzymes.1 Recent
studies in this laboratory have demonstrated the importance
of hydrosulfido complexes as precursors in the synthesis of
sulfido-bridged homo- and heterometallic clusters.2 Thus, the
dinuclear m-bis(hydrosulfido) complexes such as [(Cp*MCl)2(m-
Mo–S(1)
Mo–P(1)
Mo–P(3)
2.455(1)
2.4713(8)
2.4292(8)
77.50(3)
138.42(3)
87.00(4)
91.45(3)
130.21(3)
121.98(2)
74.09(2)
74.96(3)
Mo–S(2)
Mo–P(2)
Mo–P(4)
S(1)–Mo–P(1)
S(1)–Mo–P(3)
S(2)–Mo–P(1)
S(2)–Mo–P(3)
P(1)–Mo–P(2)
P(1)–Mo–P(4)
P(2)–Mo–P(4)
2.389(1)
2.4333(8)
2.4659(8)
85.90(3)
144.82(3)
137.73(3)
91.28(3)
75.71(2)
86.56(3)
127.73(3)
S(1)–Mo–S(2)
S(1)–Mo–P(2)
S(1)–Mo–P(4)
S(2)–Mo–P(2)
S(2)–Mo–P(4)
P(1)–Mo–P(3)
P(2)–Mo–P(3)
P(3)–Mo–P(4)
5
SH)2] (M = Ru, Rh, Ir; Cp* = h -C5Me5) and [(RuLCl)2(m-
SH)2] (L = p-arene) have turned out to be readily converted
into a variety of homo- and heterometallic m-sulfido clusters
with the nuclearities ranging from 3 to 10 by treatment with
numerous transition metal and main-group metal species.2,3
On the other hand, examples of well-defined mononuclear
bis(hydrosulfido) complexes are still limited and their transforma-
tions into sulfur-bridged multinuclear complexes have barely been
explored.1,4
Results and discussion
Preparation and characterization of 1
4
The Mo(0) complex [Mo(k -P4)(dppe)] (2; dppe = Ph2PCH2CH2-
PPh2) which is obtained from the reaction of trans-
[Mo(N2)2(dppe)2] with dppe under forcing conditions through
the condensation of two dppe ligands in the coordination sphere
of Mo,5 has been proven to react with a number of substrate
molecules to give a variety of Mo(0) and Mo(II) complexes with
In this paper, we wish to report the synthesis of
a
new bis(hydrosulfido) complex of Mo containing a linear
4
tetraphosphine co-ligand, [Mo(SH)2(k -P4)] (1; P4 = meso-o-
C6H4(PPhCH2CH2PPh2)2), and its reaction with Rh and Ir com-
plexes, affording sulfido-bridged MoRh2 and MoIr2 clusters. The
facile formation of new, early to late, Group 6 to Group 9, mixed-
metal sulfido clusters observed here are noteworthy, as it may
lead to the syntheses of a number of homo- and heterobimetallic
clusters of a new class.
4
3
the P4 co-ligand, which is bonded to the Mo center in either k , k ,
2
or k fashion.5,6 These include the formation of dihalido complexes
4
[MoX2(k -P4)] (X = Cl (3), Br) by treatment of 2 with PhCH2X,
having a trigonal-prismatic geometry rarely observed for Mo(II)
complexes.6a Now we have found that the reaction of 2 with H2S
gas in toluene at room temperature affords cleanly the Mo(II)
complex 1 as a green solid in 93% yield (Scheme 1). The structure
of 1 in the solid state has been determined by X-ray analysis using
a single crystal grown from CH2Cl2–hexane, which is shown in
Fig. 1 and Table 1.
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-
ku, Tokyo 153-8505, Japan. E-mail: ymizobe@iis.u-tokyo.ac.jp; Fax: +81-
3-5452-6361
† CCDC reference numbers 719133–719136. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b902386k
Complex 1 has a trigonal-prismatic structure analogous to
3, however, the orientation of P4 differs. Thus, as depicted in
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displays two characteristic bands assignable to n(SH) at 2537 and
2487 cm-1. For comparison, the n(SH) values of the Mo hydro-
sulfido complexes were reported for some Mo(IV) complexes, e.g.
2498 cm-1 for [Cp2Mo(SH)2],7 2480 cm-1 for [Mo(SH)(S2CNEt2)3],8
and 2568 cm-1 for [Mo(SH)( S)(dmpe)2][OSO2Me] (dmpe =
=
Me2PCH2CH2PMe2).9
On the other hand, despite the presence of two inequivalent SH
protons in the solid state, the 1H NMR spectrum of 1 in CD2Cl2 at
◦
20 C showed only one quintet at d 1.53 ppm, while the 31P{ H}
NMR spectrum at the same temperature exhibited two multiplets
of the AA¢XX¢ pattern at d 131.2 and 91.8 ppm, assignable to the
inner and outer P atoms, respectively. These spectral features may
be interpreted in terms of the pseudo rotation of the P4 ligand
around the Mo center in addition to the accidental coincidence
of the coupling constants of the SH protons with the inner P
atoms and the terminal P atoms. Although the 1H NMR spectra
were recorded at lower temperatures, only the broadening of the
SH signal was observed, indicating that 1 is still fluxional even at
-70 ◦C (vide infra).
1
It is to be noted that 1 demonstrates the first Mo(II) hy-
drosulfido complex to be fully characterized. As the related
reaction, treatment of [Mo(PMe3)6] with H2S was claimed to
result in the initial formation of [MoH2(SH)2(PMe3)4], although
Fig. 1 An ORTEP drawing for 1 at 30% probability level. Hydrogen
atoms except for the SH protons are omitted for clarity.
it was not confirmed because of its immediate conversion into
10
=
trans-[Mo( S)2(PMe3)4]. On the other hand, the W analogue
[WH2(SH)2(PMe3)4] was able to be spectroscopically character-
ized, but it was not isolable due to the similar rapid conversion
11
=
into trans-[W( S)2(PMe3)4].
Preparation and characterization of MoRh2 and MoIr2
sulfido clusters
When the bis(hydrosulfido) complex 1 was allowed to react with
one equivalent of [RhCl(CO)2]2 in CH2Cl2 in the presence of
excess NEt3 initially at -78 ◦C and then with gradual warming to
4
room temperature, a sulfido-bridged Mo(II)Rh(I)2 cluster [Mo(k -
P4)(m3-S)2{Rh(CO)2}2] (4) was isolated in 44% yield after crystal-
lization from CH2Cl2–hexane (Scheme 2). The product is a mixture
of black crystals of two different shapes and the subsequent
X-ray diffraction study of these two different shaped crystals has
revealed that the one with rhomboidal faces contains the molecule
4a shown in Fig. 2, while the other has rectangular faces consisting
of its isomer 4b depicted in Fig. 3. Interatomic distances and angles
therein are listed in Tables 2 and 3, respectively.
Scheme 1 Reactions of 2 with H2S gas (this work) and PhCH2X.6a
Scheme 1, two inner P atoms of P4 are present in the same basal
triangular plane in 1, whereas they occupy the site of different basal
planes in 3. Despite the difference in the orientation of binding,
the interatomic angles associated with P4 are almost compara-
ble: e.g., the P(1)–Mo–P(2), P(2)–Mo–P(3), P(3)–Mo–P(4), and
P(1)–Mo–P(4) angles in 1 are 75.71(2), 74.09(2), 74.96(3), and
86.56(3)◦, while those in 3 are 73.16(2), 73.30(2), 74.32(2), and
90.20(2)◦, respectively. The Mo–P bond lengths in 1 are in the
˚
Table 2 Selected interatomic distances (A) in 4a, 4b, and 5
4a (M = Rh)
4b (M = Rh)
5 (M = Ir)
M(1)–M(2)
Mo ◊ ◊ ◊ M(1)
Mo ◊ ◊ ◊ M(2)
Mo–S(1)
Mo–S(2)
Mo–P(1)
Mo–P(2)
Mo–P(3)
Mo–P(4)
M(1)–S(1)
M(1)–S(2)
M(2)–S(1)
M(2)–S(2)
2.9626(4)
3.2325(3)
3.1430(3)
2.4693(9)
2.4417(8)
2.4929(8)
2.4558(9)
2.4490(9)
2.4656(8)
2.338(1)
2.970(2)
3.208 (2)
3.281(1)
2.487(3)
2.478(3)
2.494(3)
2.415(3)
2.452(3)
2.433(3)
2.347(4)
2.320(3)
2.346(3)
2.330(3)
2.9856(6)
3.1436(7)
3.2325(8)
2.468(2)
2.452(2)
2.502(2)
2.471(2)
2.451(2)
2.479(2)
2.352(3)
2.349(2)
2.357(2)
2.339(2)
˚
range of 2.4292(8)–2.4713(8) A and are somewhat longer than
6a
˚
those of the chloro complex 3 (2.3792(7)–2.4499(5) A ), but are
not exceptional for the Mo–P bond lengths in the phosphine com-
plexes. The S–Mo–S angle in 1 at 77.50(3)◦ is slightly smaller than
the Cl–Mo–Cl angle in 3 at 81.14(2)◦, where the Mo–S(1) distance
˚
at 2.455(1) A associated with the S atom comprising the basal
2.3311(9)
2.3359(8)
2.3271(9)
plane with two terminal P atoms, P(1) and P(4), is significantly
˚
longer than the other Mo–S(2) distance at 2.389(1) A. Consistent
with this X-ray structure, the IR spectrum of 1 (KBr method)
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Scheme 2 Structures of MoRh2 and Molr2 sulfido dusters 4 and 5 in the crystalline form.
Table 3 Selected bond angles (◦) in 4a, 4b, and 5
4a (M = Rh)
4b (M = Rh)
5 (M = Ir)
Mo–S(1)–M(1)
Mo–S(1)–M(2)
Mo–S(2)–M(1)
Mo–S(2)–M(2)
M(1)–S(1)–M(2)
M(1)–S(2)–M(2)
S(1)–Mo–S(2)
P(1)–Mo–P(2)
P(1)–Mo–P(3)
P(1)–Mo–P(4)
P(2)–Mo–P(3)
P(2)–Mo–P(4)
P(3)–Mo–P(4)
S(1)–M(1)–S(2)
S(1)–M(2)–S(2)
84.46(3)
81.65(2)
85.23(2)
82.42(2)
78.67(2)
78.99(3)
78.29(2)
74.17(2)
130.91(2)
86.97(2)
74.29(2)
118.31(2)
76.17(2)
83.22(3)
83.35(3)
83.1(1)
85.5(1)
83.9(1)
86.0(1)
78.5(1)
79.4(1)
76.7(1)
73.4(11)
141.33(1)
89.2(1)
76.0(1)
105.3(1)
76.6(1)
82.6(1)
82.4(1)
84.21(9)
81.29(9)
84.61(8)
81.99(8)
78.70(8)
79.12(8)
78.95(8)
73.92(8)
131.01(8)
87.15(8)
74.32(9)
118.14(8)
76.22(8)
83.39(9)
83.52(9)
Fig. 3 An ORTEP drawing for 4b at 30% probability level. All hydrogens
as well as the phenyl carbons (except for ipso-carbons) are omitted for
clarity.
ligand in 4a is bound to Mo in a manner that the two inner
P atoms are included in the same basal triangle around Mo,
whereas in 4b the two inner P atoms are located in the different
triangular planes. These orientations of P4 in the former and
the latter correspond to those in 1 and 3, respectively. The
corresponding P–Mo–P chelating angles in 4a and 4b are well
comparable, but despite the pseudo Cs symmetrical structure for
both compounds the difference between the P(1)–Mo–P(3) and
P(2)–Mo–P(4) angles in 4b of 36◦ is much larger than that in 4a of
13◦, indicating the presence of considerable distortion with respect
to the coordination of four P atoms in 4b as compared to 4a. This
feature is also confirmed by much larger deviations of the P atoms
from the least-squares plane defined by four P atoms in 4b at
˚
+0.30, -0.36, +0.39, and -0.30 A for P(1), P(2), P(3), and P(4) in
˚
contrast to those at +0.11, -0.13, +0.13 and -0.11 A in 4a. For
comparison, these values in the less distorted 1 are +0.05, -0.06,
˚
+0.06, and -0.07 A, respectively.
Fig. 2 An ORTEP drawing for 4a at 30% probability level. All hydrogens
as well as the phenyl carbons (except for ipso-carbons) are omitted for
clarity.
˚
The Mo–Rh separations in the range 3.14–3.28 A are presumed
to be indicative of the absence of significant bonding interactions
between MoandRh atoms, while the Rh–Rhdistances at2.9625(5)
˚
Both 4a and 4b are 48-electron clusters containing one trigonal-
and 2.970(2) A in 4a and 4b, respectively, might suggest that weak
prismatic Mo(II) and two square-planar Rh(I) centers. The P4
interactions are present between the two Rh atoms.
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The IR and NMR spectra in solution recorded independently
for 4a and 4b are identical, which is interpreted in terms of the rapid
interconversion between these two structures due to the fluxional
feature involving the pseudo rotation of P4 around Mo for 4 (vide
infra).
severe broadening, but even at -70 ◦C separation of the peak was
1
not observed. The VT 31P{ H} NMR spectra of 1 are in accordance
with this finding. Thus, as shown in Fig. 5, the spectrum at
20 ◦C exhibited two multiplets of AA¢XX¢ pattern at d 131.2 and
91.8 ppm assignable to inner and terminal P atoms, respectively,
which broadened significantly as the temperature decreased, and
at -70 ◦C the signal for the inner P atoms almost coalesced.
4
The Ir analogue [Mo(k -P4)(m3-S)2{Ir(CO)2}2] (5) was prepared
from the reaction of 1 with two equivalents of [IrCl(CO)2(p-
toluidine)] according to the analogous procedure to that for
preparing 4, except that THF was used as solvent to dissolve
the latter in addition to CH2Cl2 for 1. In the case of 5, however,
isolated crystals contained only the molecule that is isostructural
with 4a (Scheme 2). The ORTEP drawing is shown in Fig. 4, while
the selected interatomic distances and angles are listed in Tables 2
and 3. The Ir–Ir and Ir–S distances in 5 are longer than the Rh–Rh
and Rh–S distances in 4a, but only slightly, and the deviations of
P atoms of P4 from the least-squares plane defined by these four P
˚
atoms at +0.10, -0.16, +0.16, and -0.10 A observed for P(1), P(2),
P(3), and P(4) are almost identical with those for 4a.
1
Fig. 5 VT 31P{ H} NMR spectra of 1 in CD2Cl2.
1
VT 31P{ H} NMR studies were also conducted for 4 and 5.
Although 4 exists as two isomeric forms in the solid state as
described above, their spectral features in solution are the same.
1
Fig. 6 depicts the 31P{ H} NMR spectra of 4, which indicates
that by lowering the recording temperature to -70 ◦C both of the
two signals due to the inner and terminal P atoms separated into
two signals, indicating the presence of two slowly interconverting
species at this temperature. This is consistent with the finding about
the solid state structures of 4 by X-ray analysis. Similar spectral
features were also observed for the Ir analogue 5 as shown in Fig. 7,
although two signals assignable to the inner and terminal P atoms
are still quite broad even at -70 ◦C. Based on the structures of two
isomers demonstrated for 4 in a well-defined manner by the X-ray
analysis, the fluxional feature of 1, 4, and 5 may be interpreted
by the rotation of the P4 ligand occurring around the Mo center,
which is shown in Scheme 3.
Fig. 4 An ORTEP drawing for 5 at 30% probability level. All hydrogens
as well as the phenyl carbons (except for ipso-carbons) are omitted for
clarity.
The IR spectrum of 5 in CH2Cl2 displayed three characteristic
n(CO) bands at 2032, 2010, and 1959 cm-1, which are considerably
lower than those of the Rh analogue 4 at 2043, 2024, and 1976 cm-1,
as expected from the greater electron-donating ability of the
Ir(I) center than Rh(I). This difference corresponds well to that
observed previously between [Cptt Zr(m3-S)2{Rh(CO)2}2] (Cptt =
2
5
h -1,3-tBu2C5H3) and its Ir analogue: 2066, 2041, and 1994 cm-1
for the former and 2056, 2027, and 1979 cm-1 for the latter.4h
1
The 31P{ H} NMR spectrum recorded at room temperature is
essentially similar to that of 4 and the VT NMR study has revealed
the fluxional behavior for 5 as described below.
Fluxional feature of 1, 4, and 5 in solution
As demonstrated by X-ray analysis, two SH protons in 1 are
inequivalent in the solid form. However, these protons are recorded
1
in its H NMR spectrum at room temperature as one quintet at
d 1.53 ppm, indicating the fluxional nature of 1 in solution. As the
recording temperature was lowered to -10, -40, and -70 ◦C, this
signal gradually shifted towards the higher field with concurrent
1
Fig. 6 VT 31P{ H} NMR spectra of 4 in CD2Cl2.
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and the mixture was stirred continuously for 2 h under H2S
atmosphere. A green solid precipitated, which was filtered off,
washed with toluene (20 mL ¥ 2) and ether (20 mL ¥ 5), and
then dried in vacuo. Complex 1 was obtained as a green powder
(1.14 g, 93% yield). Single crystals suitable for X-ray diffraction
were obtained by crystallization of the solid from CH2Cl2–hexane.
Anal. Found: C, 62.92; H, 5.02. C46H44MoP4S2 requires C, 62.73;
H, 5.04. IR (KBr): n(SH) 2537, 2487 cm-1. dH (400 MHz; CD2Cl2,
20 ◦C): 7.85–7.75, 7.65–7.55 (m, 2H each, aromatic), 7.3–7.0 (m,
22H, aromatic), 6.91 (t, 4H, aromatic), 6.7–6.6 (m, 4H, aromatic),
2.45–2.25 (br, 2H, PCH2), 2.1–1.7 (br, 6H, PCH2), 1.53 (quint, J =
2.2 Hz, 2H, SH). dP (162 MHz, CD2Cl2, 20 ◦C): 131.2 (m, 2P, inner
P), 91.8 (m, 2P, outer P), AA¢XX¢ pattern: JAX + JAX¢ = 30 Hz.
1
Fig. 7 VT 31P{ H} NMR spectra of 5 in CD2Cl2.
Synthesis of 4. Complex 1 (441 mg, 0.500 mmol) and
[RhCl(CO)2]2 (195 mg, 0.501 mmol) were dissolved in CH2Cl2
(30 mL) and then NEt3 (280 mL, 2.01 mmol) was added at
-78 ◦C. The mixture was gradually warmed to room temperature
with stirring. After 18 h, the solution was concentrated to ca. 5 mL
in vacuo and the resultant mixture was filtered to give a dark
green solid and a green filtrate. The solid was washed with CH2Cl2
(5 mL ¥ 2) and dried, while the filtrate was concentrated again to
ca. 3 mL and the mixture was filtered off. The solid remained,
which was washed with CH2Cl2 (2 mL ¥ 2) and dried. Two
crops of crude product were combined and crystallized from
CH2Cl2–hexane, yielding 4 as black crystals (263 mg, 44%). These
consisted of thin rhomboidal crystals containing 4a and thin
rectangular crystals containing 4b, where large crystals were able to
be separated manually. Anal. for the mixture of 4a and 4b. Found:
C, 50.01; H, 3.39. C50H42O4MoP4Rh2S2 requires C, 50.19; H, 3.54.
The data below recorded independently for 4a and 4b are the same.
IR (CH2Cl2): n(CO) 2043, 2024, 1976 cm-1. dH (400 MHz; CD2Cl2,
20 ◦C): 7.85 (br, 4H, aromatic), 7.76 (br, 2H, aromatic), 7.5–7.3 (m,
10H, aromatic), 7.2–7.1 (m, 10H, aromatic), 6.99 (t, 4H, aromatic),
6.62 (br, 4H, aromatic), 2.87, 2.29, 2.20, 1.43 (br, 2H each, PCH2).
dP (162 MHz, CD2Cl2, 20 ◦C): 118.8 (br, 2P, inner P), 81.9 (br, 2P,
outer P).
Synthesis of 5. A solution of [IrCl(CO)2(p-toluidine)] (392 mg,
1.00 mmol) and NEt3 (280 mL, 2.01 mmol) in THF (10 mL)
cooled to -78 ◦C was poured into a stirred solution of 1 (441 mg,
0.500 mmol) in CH2Cl2 (20 mL) at -78 ◦C. The solution was
stirred continuously with gradual warming to room temperature,
affording a green suspension. The product mixture was filtered off
and the green solid obtained was washed with CH2Cl2 (5 mL ¥ 3).
Drying in vacuo of the residue gave analytically pure 5 (519 mg,
76% yield). Single crystals for X-ray analysis were available by
recrystallization from CH2Cl2–hexane. Found: C, 43.81; H, 3.04.
C50H42O4MoP4Ir2S2 requires C, 43.67; H, 3.08. IR (CH2Cl2):
n(CO) 2032, 2010, 1959 cm-1. dH (400 MHz; CD2Cl2, 20 ◦C):
7.83 (br, 4H, aromatic), 7.76, 7.50 (br, 2H each, aromatic), 7.38
(m, 8H, aromatic), 7.23 (m, 6H, aromatic), 7.13, 7.03 (t, 4H each,
aromatic), 6.59 (br, 4H, aromatic), 2.62,◦2.11, 2.03, 1.54 (br, 2H
each, PCH2). dP (162 MHz, CD2Cl2, 20 C): 116.0 (m, 2P, inner
P), 76.3 (m, 2P, outer P).
Scheme 3 Fluxional feature observed for 1, 4, and 5 due to the rotation
of the P4 ligand around Mo.
Experimental
General comments
All manipulations were carried out under N2 using standard
Schlenk techniques. Solvents were dried by common methods and
distilled under N2 before use. Complexes 2,5 [RhCl(CO)2]2,12 and
[IrCl(CO)2(p-toluidine)]13 were prepared according to literature
procedures, while the chemicals were obtained commercially and
used as received except for NEt3, which was treated with KOH and
distilled under N2 before use.
IR spectra were recorded on a JASCO FT/IR-420 spectrometer,
1
while 1H and 31P{ H} NMR spectra were obtained from a JEOL
alpha-400 spectrometer. Elemental analyses were performed with
a Perkin-Elmer 2400 series II CHN analyzer.
Preparation of complexes
X-Ray crystallography†
Synthesis of 1. Through a stirred suspension of 2 (1.80 g,
Details of diffraction studies are summarized in Table 4. Single
1.39 mmol) in toluene (50 mL), H2S gas was bubbled for 15 min,
crystals of 1, 4a·1.3CH2Cl2, 4b·0.5CH2Cl2, and 5·1.375CH2Cl2
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Table 4 Crystal data for 1, 4a, 4b, and 5
1
4a·1.3CH2Cl2
4b·0.5CH2Cl2
5·1.375CH2Cl2
Formula
Mr
C46H44P4S2Mo
880.81
C51.6H45.2O4P4S2Cl3.2MoRh2
1332.54
C50.5H43O4P4S2ClMoRh2
1239.11
C51.38H44.75O4P4S2Cl2.75MoIr2
1492.12
Monoclinic
C2/c (no. 15)
41.213(9)
12.066(2)
21.619(4)
95.852(1)
10 695(4)
8
1.853
0.50 ¥ 0.20 ¥ 0.10
54.96
293
12 245
5474
638
Crystal system
Space group
Monoclinic
P21/c (no. 14)
14.054(3)
12.073(2)
25.259(5)
103.749(1)
4163(2)
4
1.405
0.40 ¥ 0.20 ¥ 0.10
55.74
293
9892
5700
528
Monoclinic
C2/c (no. 15)
41.234(1)
11.9799(4)
21.7291(9)
96.1025(7)
10 673.0(7)
8
1.658
0.10 ¥ 0.10 ¥ 0.10
54.96
293
12 020
8735
638
Monoclinic
P21/c (no. 14)
13.709(4)
17.143(4)
20.980(5)
101.070(1)
4839(2)
˚
a/A
˚
b/A
˚
c/A
b/◦
3
˚
V/A
Z
4
Dc/Mg m-3
1.701
0.50 ¥ 0.20 ¥ 0.10
54.96
293
11 062
5033
624
Crystal size/mm3
◦
2qmax
T/K
/
Unique reflections
Data of I > 2s(I)
Variables
Transmission factor
0.643–1.000
0.038
0.130
0.586–0.883
0.037
0.114
0.661–0.883
0.063
0.201
0.293–0.572
0.049
0.177
a
R1
wR2
b
GOFc
1.013
1.018
1.076
1.032
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
a R1 = ꢀFo| - |Fcꢀ/ |Fo| (I > 2s(I)). b wR2 = [ (w(Fo - Fc2)2)/ w(Fo2)2]1/2 (all data). c GOF = [ w(|Fo| - |Fc|)2/{(no. observed) - (no.
2
variables)}]1/2
.
were sealed in glass capillaries under argon and mounted on a
Rigaku Mercury-CCD diffractometer equipped with a graphite-
monochromatized Mo Ka source. Data collections were per-
formed by using the CrystalClear program package.14 All data
were corrected for absorption.
Catalysis”) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan.
References
Structure solution and refinements were conducted by us-
ing the Crystal Structure program package.15 The positions of
non-hydrogen atoms were determined by Patterson methods
(PATTY)16 and subsequent Fourier synthesis (DIRDIF99),17
which were refined by full-matrix least-squares techniques. Hy-
drogen atoms were placed at the calculated positions and included
at the final stages of the refinements with fixed parameters.
For 1, the SH hydrogens were found in the Fourier map and
refined isotropically. In 4a·1.3CH2Cl2, two CH2Cl2 molecules
are disordered, where the population of the molecule near the
2-fold axis is 0.6. All non-hydrogen atoms in these molecules were
refined isotropically, while hydrogens were not added. Some C–Cl
bonds were restrained. For 4b·0.5CH2Cl2, the solvating CH2Cl2
molecules, which are present around the inversion center, are
disordered and their structures were refined isotropically with
restraints of bond lengths and angles with hydrogens at the
calculated positions. In 5·1.375CH2Cl2, both solvating CH2Cl2
molecules are disordered, for which the Cl atoms were refined
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Hydrogens were not included. The population of the molecule
near the 2-fold axis was found to be 0.75. For the other molecule,
refinements were carried out with the restrained C–Cl bonds.
CCDC numbers are 719133–719136 for 1, 4a·1.3CH2Cl2,
4b·0.5CH2Cl2, and 5·1.375CH2Cl2, respectively.
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Acknowledgements
This work was supported by the Grant-in-Aid for Scientific Re-
search on Priority Areas (No. 18065005, “Chemistry of Concerto
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 6134–6140 | 6139
©

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6140 | Dalton Trans., 2009, 6134–6140
This journal is
The Royal Society of Chemistry 2009
©