The reaction of triosmium and -ruthenium clusters with bifunctional ligands

Article abstract of DOI:10.1016/j.jorganchem.2008.01.025

The reaction of [Os₃(CO)₁₀(μ-H)(μ-OH)], 1, or [Os₃(CO)₁₀(NCCH₃)₂], 2, with bifunctional ligands carrying -OH, -SH and -COOH groups affords, as the major product, clusters of the general formula [Os₃(CO)₁₀(μ-H)(μ-E^{frown}E′H)] (E, E′ = O, S or COO). In some cases, a minor product with general formula [Os₃(CO)₁₀(μ-H)(μ,μ-E^{frown}E′)Os₃(CO)₁₀(μ-H)] was also obtained. With Ru₃(CO)₁₂, 3b, only the first type of products is obtained. The structures of eight of the compounds have also been determined by single crystal X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2008.01.025

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 1292–1300
www.elsevier.com/locate/jorganchem
The reaction of triosmium and -ruthenium clusters
with bifunctional ligands
Chunxiang Li, Weng Kee Leong *
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Received 15 October 2007; received in revised form 14 January 2008; accepted 15 January 2008
Available online 20 January 2008
Abstract
The reaction of [Os3(CO)10(l-H)(l-OH)], 1, or [Os3(CO)10(NCCH3)2], 2, with bifunctional ligands carrying –OH, –SH and –COOH
groups affords, as the major product, clusters of the general formula [Os3(CO)10(l-H)(l-E_E0H)] (E, E0 = O, S or COO). In some cases, a
minor product with general formula [Os3(CO)10(l-H)(l,l-E_E0)Os3(CO)10(l-H)] was also obtained. With Ru3(CO)12, 3b, only the first
type of products is obtained. The structures of eight of the compounds have also been determined by single crystal X-ray crystallography.
Ó 2008 Elsevier B.V. All rights reserved.
Keywords: Osmium; Ruthenium; Bifunctional ligand; Cluster
1. Introduction
various alcohols to form hydridoalkoxy and dialkoxy-
derivatives with the general formulae [Os3(CO)10(l-H)(l-
OR)] and [Os3(CO)10(l-OR)2], respectively [4]; and with
thiols and carboxylic acids to form hydridothiolato or
hydridocarboxylato derivatives, respectively [5]. The reac-
tions of 2 with thiolate–carboxylic acids and dicarboxylic
acids have been reported to afford linked clusters with
the general formula [{Os3(CO)10(l-H)}2(l-L0)] [6], while
its reactions with HSCH2CH2SH and diols afforded
clusters with only one triosmium moiety, viz., [Os3(CO)10-
(l-H)(l-SCH2CH2SH)] and [Os3(CO)10(l-H){l-O(CH2)n-
OH}], respectively. Interestingly though, the reaction
of 2 with 1,3-propanedithiol afforded the linked cluster
[{Os3(CO)10(l-H)}2(l,l,g2-SCH2CH2CH2S)] only [6e].
Similarly, the reaction of [Ru3(CO)12], 3b, with HSCH2-
COOH gave only [Ru3(CO)10(l-H)(l-SCH2COOH)]
[7].
Organometallic clusters are of interest as precursors for
the deposition of molecular clusters [1] and size-controlled
metallic particles [2]. A useful method for the deposition of
molecular clusters onto surfaces is via a linking group
between the surface and the cluster. We recently reported
the use of time-of-flight secondary ion mass spectrometry
(ToF-SIMS) as a means to examine such surface species
[3], and in extending that study, we attempted to synthesise
some clusters which have a ligand that can be used for
anchoring onto various surfaces through the reaction of
some precursor clusters with bifunctional ligands. The syn-
thesis and characterisation of these clusters are described
here.
2. Results and discussion
We have found that the reaction of 1 in refluxing toluene,
or 2 at ambient temperature in dichloromethane, with
bifunctional ligands afforded two types of clusters (Scheme
1) [8]. The major product is of the general formula
[Os3(CO)10(l-H)(l-E_E0H)] (type A). In some cases, a
minor product with general formula [Os3(CO)10(l-H)-
(l,l-E_E0)Os3(CO)10(l-H)] (type B) was also obtained.
The reaction of 1 with 2,5-dimercapto-1,3,4-thiadiazol
2.1. Reaction of triosmium and -ruthenium clusters with
bifunctional ligands
The triosmium clusters [Os3(CO)10(l-H)(l-OH)], 1, or
[Os3(CO)10(NCCH3)2], 2, have been reported to react with
*
Corresponding author.
E-mail address: chmlwk@nus.edu.sg (W.K. Leong).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.01.025

C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
1293
afforded a cluster with a more complex bonding mode, viz.
two triosmium moieties bridged by thiolato-carboxylato
ligands (15b, 17b and 18b), their IR spectra showed a more
complicated pattern, which can be regarded as the overlap
of a thiolato-bridged Os3(CO)10(l-H) moiety, which has
the highest energy band at 2108–2110 cmꢀ1, and a carboxy-
lato-bridged Os3(CO)10(l-H) moiety, which has the highest
, 8.
With the exception of 8, 15b, 17b and 18b, all the other
clusters exhibit similar patterns in the carbonyl region of
their IR spectra, which are comparable to those of other
triosmium clusters of the type [Os3(CO)10(l-H)(l-SR)],
indicating that the metal core of these products are struc-
turally similar [4–6]. In the case of products containing
energy band at 2113–2114 cmꢀ1
.
The hydride resonances in the 1H NMR spectra are also
characteristic – the thiolato-, carboxylato- and alkoxy-
E'
E E'H
+
E
Os
OH
Os
Os
Os
H
H
H
+
HE E'H
H
Os
Os
Os
Os
Os
Os
type
Os
Os
1
A
type
B
4a (58 %)
HS(CH2)3SH
5a (63 %)
6a (37 %)
5b (3 %)
HS
SH
CH2SH
HSCH2
7a (61 %)
9a (95 %)
10a (53 %)
11a (32 %)
HS(CH2)8SH
7b (13 %)
HSCH2CH2OH
HSCH2CH2CH2OH
HS CH2OH
HS(CH2) OH
11
12a (10 %), 12a' (8 %)*
13a (77 %)
12b (1 %)
HSCH2COOH
HS(CH2)10 COOH
17a (44 %)
17b (4 %)
18b (3 %)
21b (3 %)
18a (46 %)
HS(CH2)15 COOH
HO(CH2)12 OH
21a (48 %)
* for 12a’, E = O, E’ = S.
L'
L L'H
Os
L
Os
Os
Os
MeCN
Os
H
or
H
+ HL L'H
Os
H
Os
Os
Os
Os
Os
Os
NCMe
2
type A
type
B
HS(CH2)2COOH
14a (64 %)
15a (73 %)
15b (3 %)
COOH
COOH
HS
HS
16a (68 %)
19a (73 %)
HOOC(CH2)10OH
HO(CH2)4OH
20a (52 %)
Scheme 1.

1294
C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
bridged clusters exhibited hydride resonances at about
ꢀ17, ꢀ10, and ꢀ12 ppm, respectively. The hydride reso-
nances for those containing an aromatic ring are also
shifted upfield by about 0.3–0.7 and 0.3 ppm, for the thio-
lato- and carboxylato-bridged clusters, respectively, com-
pared to the alkyl analogues.
and 5b are shown in Figs. 1 and 2, respectively. The overall
structure of 5b is very similar to that of the methanedithio-
lato and propanedithiolato analogues [{Os3(CO)10(l-
H)}2(l,l,g2-SCH2S)] and [{M3(CO)10(l-H)}2(l,l,g2-
SCH2CH2CH2S)] (M = Os, Ru) [6a,6e]. Structurally, 5b is
equivalent to two moieties of 5a.
Although the relative yields of the type B clusters are
low compared to the type A clusters, their formation
appears to depend on the nature of the ligand. Formation
of the type B clusters is less likely with a shorter methylene
chain, presumably due to the steric problem associated
with having two clusters connected via a short chain. More
importantly perhaps, the propensity of the functional
groups to bond to the cluster also shows a very clear trend
in the order: SH > COOH > OH. This can be seen in that
bifunctional ligands containing an SH and an OH or
COOH group afforded almost exclusively type A clusters
with the thiolate bridge (9–11a and 13–18a), and the ligand
HO(CH2)10COOH afforded a type A cluster with the car-
boxylate bridge (19a). The type B clusters were presumably
formed via the intermediacy of the type A clusters; the
room temperature reaction of HSCH2CH2COOH with
two equivalents of 2 afforded 14a (21%) and the previously
reported linked cluster [Os3(CO)10(l-H)(l,l-SCH2CH2-
COO)Os3(CO)10(l-H)], 14b (11%) [6]. In addition, the reac-
tion of 14a with 2 also afforded 14b.
Selected bond parameters and a common atomic num-
ber scheme for 5a, 5b, 9a, 13a, 14a, and 15a are shown in
Table 1. The bond parameters are unexceptional; there is
no obvious trend observable for the Os–Os bond distances,
even between the thiolato-bridged Os–Os bond and the
others, and these Os–Os bond distances as well as the
Os–S distances are similar to those in related clusters [9].
Compound 15b is a type B cluster in which E ¼ E0. The
molecular structure of 15b and selected bond parameters
˚
are given in Fig. 3. The Os(4)–Os(5) bond [2.9244(10) A],
which is bridged by the carboxylate group, is longer than
the others; this effect is well-documented [6].
The structure of 8 is shown in Fig. 4, together with
selected bond parameters. It is structurally similar to 5b,
except that an additional nitrogen atom has also coordi-
nated to one of the triosmium moiety in place of a
˚
carbonyl. The Os(1)–Os(2) distance [2.8067 A] in this par-
ticular unit is shorter compared to the others in the same
˚
cluster [2.8413(9)–2.8503(10) A], while the thiolato-bridged
Os–Os bond length is again similar to those of structurally
In a similar set of reactions with [Ru3(CO)12], 3b, only
clusters of type A were obtained (Scheme 2). The IR spec-
tra of the products also showed patterns in the metal car-
bonyl region that are similar to the osmium analogues,
and the metal hydride resonances are at about ꢀ15 ppm,
which indicated that it is the SH moiety which has reacted
with the triruthenium core [7].
2.2. Crystallographic studies
Five clusters of type A (5a, 9a, 13a, 14a, and 15a) and
two of type B (5b and 15b), together with 8, were character-
ised crystallographically. The molecular structures of 5a
S
COOH
Ru
Ru
Fig. 1. ORTEP diagram for 5a; thermal ellipsoids were drawn at the 50%
+
HS
COOH
probability level and aromatic hydrogens have been omitted.
H
Ru
Ru
Ru
Ru
3b
type
A
HS(CH2)2COOH
14a(Ru) (31 %)
15a(Ru) (61 %)
HS
HS
COOH
COOH
16a(Ru) (27 %)
17a(Ru) (43 %)
18a(Ru) (80 %)
HS(CH2)10COOH
HS(CH2)15COOH
Fig. 2. ORTEP diagram for 5b. Thermal ellipsoids were drawn at the 50%
Scheme 2.
probability level and aromatic hydrogens have been omitted.

C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
1295
Table 1
˚
Common atomic numbering scheme and selected bond lengths (A) and bond angles (°) for 5a, 5b, 9a, 13a, 14a and 15a
S(4)
C(1)
Os(1)
Os(3)
H
Os(2)
5a
5b
9aa
13a
14ab
15a
˚
Bond length (A)
Os(1)–Os(2)
Os(2)–Os(3)
Os(3)–Os(1)
Os(1)–S(4)
Os(2)–S(4)
S(4)–C(1)
2.8628(2)
2.8571(4)
2.8841(4), 2.8576(4)
2.8347(4), 2.8516(4)
2.8349(4), 2.8467(4)
2.4102(16), 2.4123(17)
2.4124(16), 2.4061(16)
1.828(6), 1.835(7)
2.8546(4)
2.857(7)
2.8694(4)
2.8628(2)
2.8462(2)
2.4171(10)
2.4171(10)
1.793(4)
2.8565(4)
2.8658(5)
2.4185(18)
2.4153(18)
1.779(8)
2.8563(4)
2.8483(4)
2.4059(18)
2.4063(19)
1.836(8)
2.851(6)
2.848(5)
2.403(5)
2.406(9)
1.835(13)
2.8418(4)
2.8544(4)
2.4119(16)
2.4123(16)
1.788(6)
Bond angle (°)
Os(1)–S(4)–Os(2)
72.63(3)
72.47(5)
73.46(4), 72.75(5)
72.77(5)
72.9(3)
73.00(5)
a
Two crystallographically independent molecules.
Values for 14a are averaged over the five crystallographically independent molecules; e.s.d.s are over the sample size of five molecules.
b
˚
Fig. 4. ORTEP diagram and selected bond lengths (A) and angles (°) for
8. Thermal ellipsoids were drawn at the 50% probability level. Selected
Fig. 3. ORTEP diagram for 15b. Thermal ellipsoids drawn at the 50%
probability level and organic hydrogens have been omitted. Selected bond
˚
bond lengths (A) and bond angles (°): Os(1)–Os(2) 2.8067(10), Os(2)–Os(3)
˚
lengths (A) and bond angles (°): Os(1)–Os(2) 2.8708(7), Os(2)–Os(3)
2.8318(10), Os(3)–Os(1) 2.8083(10), Os(4)–Os(5) 2.8464(9), Os(5)–Os(6)
2.8413(9), Os(6)–Os(4) 2.8503(10), Os(1)–S(1) 2.426(5), Os(2)–S(1)
2.453(4), Os(4)–S(2) 2.413(4), Os(5)–S(2) 2.417(2), S(1)–C(1) 1.733(17),
S(2)–C(2) 1.791(17), Os(1)–S(1)–Os(2) 70.23(12), Os(4)–S(2)–Os(5)
72.11(11).
2.8746(8), Os(3)–Os(1) 2.8450(7), Os(4)–Os(5) 2.9244(10), Os(5)–Os(6)
2.8659(7), Os(6)–Os(4) 2.8758(8), Os(1)–S(1) 2.418(3), Os(2)–S(1) 2.426(3),
Os(4)–O(71) 2.131(7), Os(5)–O(72) 2.150(7), S(1)–C(1) 1.807(10), Os(1)–
S(1)–Os(2) 72.69(8).
similar clusters such as [Os3(CO)9(l-H)(l-pyS)] and
[{Os3(CO)9(l-H)}(l-SC5H3NCO2){Os3(CO)10(l-H)}] [10,9b].
afforded only triruthenium clusters of the type [Ru3-
(CO)10(l-H)(l-L_COOH)].
4. Experimental
3. Conclusion
4.1. General procedure
In conclusion, we have found that the reaction of the
clusters Os3(CO)10(l-H)(l-OH) or Os3(CO)10(NCCH3)2
with bifunctional ligands HE_E0H gave as the major prod-
ucts, clusters with the general formula [Os3(CO)10(l-H)(l-
E_E0H)]. The propensity towards binding of the functional
group E with the cluster follows the order: SH > COO-
H > OH. When the ligand contains an aromatic ring or a
long methylene chain spacer, the formation of clusters con-
taining two triosmium moieties linked by the ligand, viz.,
[{Os3(CO)10(l-H)}2(l-L_L0)], increased. In contrast, the
reaction of [Ru3(CO)12] with mercaptocarboxylic acids
All reactions were carried out using standard Schlenk
techniques under an argon or nitrogen atmosphere. Sol-
vents that were used for reactions were distilled over the
appropriate drying agents under nitrogen and kept in flasks
provided with Teflon valves before use. Reaction mixtures
1
were separated by TLC. H NMR spectra were recorded
on a Bruker ACF-300 FT-NMR spectrometer. The solvent
used was deuterated chloroform. FAB-MS were obtained
with a HP6890 GC system. Elemental analyses were carried
out on a Perkin–Elmer PE 2400 CHN or CHNS Elemental

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C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
Table 2
Spectroscopic and analytical data for the type A osmium clusters
Compound IR (hexane) mCO (cmꢀ1
)
FAB (m/z) [M+]: 1H d (ppm in CDCl3)
Calc. (Found)
Elemental Anal. (%) Calc.
(Found)
3
4a
2109w, 2067vs, 2058s, 2021vs, 1996m, 959 (960)
1987w
2.62 (q, JHH = 8.3 Hz, 2H, CH2SH), 2.47 (t,
3JHH = 7.4 Hz, 2H, SCH2), 1.94 (quintet, 2H,
C,16.28 (16.75); H, 0.84
(0.85); S, 6.69 (6.98)
3
SCH2CH2), 1.39 (t, JHH = 8.3 Hz, SH), ꢀ17.40
(s, 1H, OsHOs)
5a
6a
2110w, 2071s, 2059m, 2023s, 2000m, 993 (994)
7.23–7.01 (m, 4H, Ph), 3.47 (s, 1H, SH), ꢀ17.05 (s, C, 19.35 (19.80); H, 0.61
1998wa
1H, OsHOs)
(0.63); S, 6.46 (6.13)
3
2109w, 2067s, 2058m, 2022s, 1997w, 1021 (1020)
1981wa
7.27 (d, JHH = 10.7 Hz, 4H, Ph), 3.71 (d,
3JHH = 7.4 Hz, 2H, CH2SH), 3.58 (s, 2H, SCH2),
1.73 (t, 1H, SH), ꢀ17.38 (s, 1H, OsHOs)
3
7a
2109m, 2067vs, 2058s, 2026vs, 2019s, 1029 (1028)
1999m, 1989m, 1983w
2.50 (q, JHH = 7.4 Hz, 2H, CH2SH), 2.35 (t, 2H, C, 21.01 (21.28); H, 1.76
SCH2), 1.63 (m, 5H, SCH2CH2, CH2CH2SH, SH), (2.03); S, 6.23 (6.04)
1.30–1.47 (m, 8H, SCH2CH2(CH2)4CH2CH2SH),
ꢀ17.40 (s, 1H, OsHOs)
8
2114w, 2088m, 2075vs, 2067s, 2030vs, 1823 (1824)
2003s, 1958w
2109w, 2068s, 2059m, 2025s, 2020sh, 929 (930)
2001w, 1990w, 1984w
2108w, 2067vs, 2057m, 2021s, 1995w, 945 (944)
1980w
ꢀ16.93 (s, H, OsHOs), ꢀ11.70 (s, 1H, OsHOs)
3
9a
10a
3.85 (t, JHH = 5.8 Hz, 2H, CH2OH), 2.62 (t, 2H, C, 15.52 (15.51); H, 0.65
SCH2), 1.74 (t, 1H, OH), ꢀ17.36 (s, 1H, OsHOs) (0.79); S, 3.45 (3.01)
3
3.77 (q, JHH = 2.8 Hz, 2H, CH2OH), 2.49 (t,
3JHH = 5.0 Hz, 2H, SCH2), 1.87 (quintet, 2H,
SCH2CH2), 1.34 (t, 1H, OH), ꢀ17.38 (s, 1H,
OsHOs).
C, 16.56 (16.44); H, 0.86
(0.89); S, 3.57 (3.40)
3
11a
12a
2110w, 2069vs, 2057vs, 2024s, 1999m, 991 (992)
1967w
2109w, 2069vs, 2058m, 2020s, 1998w, 1054 (1055)
1980w
7.32–7.40 (m, 3H, Ph), 6.82 (d, JHH = 7.4 Hz,
C, 20.60 (20.32); H, 0.81
1H, Ph), 5.09 (s, 2H, CH2) ꢀ16.92 (s, 1H, OsHOs) (0.78); S, 3.24 (2.91)
3
3.63 (t, JHH = 6.6 Hz, 2H, CH2OH), 2.35 (t,
3JHH = 8.2 Hz, 2H, SCH2), 1.54 (m, 4H,
SCH2CH2, CH2CH2OH), 1.27 (m, 14H,
SCH2CH2(CH2)7CH2CH2OH), ꢀ17.40 (s, 1H,
OsHOs)
C, 23.90 (24.32); H, 2.29
(2.14); S, 3.04 (2.84)
3
12a0
2108w, 2066vs, 2057m, 2021s, 1997w, 1054 (1057)
1983w
3.52 (t, JHH = 6.6 Hz, 2H, CH2O), 2.67 (t,
7.4 Hz, 2H, HSCH2), 1.54 (m, 4H, SCH2CH2,
CH2CH2OH), 1.27 (m, 14H,
SCH2CH2(CH2)7CH2CH2OH), ꢀ12.53 (s, 1H,
OsHOs)
13a
14a
15a
2111w, 2070s, 2060m, 2023s, 1999wa 942 (941)
3.21 (s, 2H, CH2), ꢀ17.36 (s, 1H, OsHOs)
C, 15.29 (15.63); H, 0.43
(0.78); S, 3.40 (3.29)
C, 16.32 (16.54); H, 0.63
(0.62); S, 3.35 (3.49)
2112w, 2071s, 2061m, 2026vs, 2021 m 957 (958)
(sh), 2001m, 1989w, 1984w
2110w, 2069s, 2060m, 2024vs, 2001m, 1005 (1005)
1982w
2.74-2.87 (m, 4H, CH2CH2), ꢀ17.30 (s, 1H,
OsHOs)
3
8.0 (s, 1H, Ph), 7.96 (d, JHH = 7.4 Hz, 1H, Ph), C, 20.32 (20.18); H, 0.60
7.56 (d, JHH = 9.1 Hz, 1H, Ph), 7.41 (t, 1H, Ph), (0.65); S, 3.19 (3.12)
3
ꢀ16.98 (s, 1H, OsHOs)
16a
17a
2110w, 2070s, 2060m, 2024vs, 2001m, 1005 (1006)
1982wa
2108w, 2066vs, 2057m, 2024s, 2020s, 1070 (1072)
1996m, 1989w, 1982w
8.04 (d, 3JHH = 8.2 Hz, 2H, Ph), 7.39 (d, 2H, Ph),
ꢀ7.06 (s, 1H, OsHOs)
2.35 (m, 4H, SCH2, CH2COOH), 1.65 (m, 4H,
SCH2CH2, CH2CH2COOH), 1.27 (m, 12H,
SCH2CH2(CH2)6), ꢀ17.41 (s, 1H, OsHOs)
C, 23.59 (23.56); H, 2.07
(1.70); S, 3.00 (3.07)
3
18a
19a
2108w, 2066vs, 2057m, 2021vs,
1996w, 1982wa
1139 (1140)
3.63 (t, JHH = 6.6 Hz, 2H, SCH2), 2.35
C, 27.41 (27.40); H, 2.83
(t,3JHH = 8.2 Hz, 2H, CH2COOH), 1.54 (m, 4H, (2.25); S, 2.81 (2.87)
SCH2CH2, CH2CH2COOH), 1.24 (m, 22H,
SCH2CH2(CH2)11), ꢀ17.41 (s, 1H, OsHOs)
3
2113w, 2074vs, 2062s, 2024vs, 2014s, 1067 (1068)
1981w
3.63 (t, JHH = 6.6 Hz, 2H, CH2OH), 2.18 (t,
3JHH = 7.4 Hz, 2H, CH2COO), 1.54 (m, 4H,
HOCH2CH2, OOCCH2CH2), 1.22 (m, 14H,
HOCH2CH2(CH2)7CH2CH2COOH), ꢀ10.51 (s,
1H, OsHOs)
C, 24.76 (25.22); H, 2.27
(2.49)
20a
21a
2109w, 2067vs, 2058s, 2025vs, 1988w 941 (942)
3.57 (m, 4H, CH2(CH2)2CH2), 1.53 (m, 4H,
CH2(CH2)2CH2)
3.63 (t, JHH = 6.6 Hz, 2H, CH2OH), 3.51 (t,
3JHH = 6.6 Hz, 2H, OCH2) 1.45 (m, 4H,
HOCH2CH2, OCH2CH2), 1.23 (m, 16H,
HOCH2CH2(CH2)8), ꢀ12.53 (s, 1H, OsHOs)
C, 17.87 (18.26); H, 1.07
(1.14)
C, 25.09 (24.67); H, 2.49
(2.53)
3
2109w, 2069vs, 2058s, 2020vs, 1997m, 1053 (1054)
1977w
a
IR spectrum was recorded in dichloromethane.

C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
1297
Table 3
Spectroscopic and analytical data for the type B osmium clusters
Compound
IR (CH2Cl2) mCO (cmꢀ1
)
FAB (m/z)
[M+]: Calc.
(Found)
1H d (ppm in CDCl3)
3
5b
7b
2109w, 2071s, 2061m, 2027vs, 2021sh,
2004w
2108w, 2066vs, 2057m, 2020vs, 1998m
1844 (1843)
7.42 (s, 1H, Ph), 7.32 (t, JHH = 8.3 Hz, 1H, Ph), 7.03 (d, 2H, Ph),
ꢀ17.05 (s, 1H, OsHOs)
2056 (2056)
2.67 (t, 3JHH = 6.6 Hz, 2H, CH2S), 2.35 (t, 3JHH = 7.4 Hz, 2H, SCH2),
1.66 (quintet, 4H, SCH2CH2), 1.32 (m, 8H,
SCH2CH2(CH2)4CH2CH2SH), ꢀ17.40 (s, 1H, OsHOs)
3.52 (t, 3JHH = 7.4 Hz, 2H, CH2O), 2.35 (t, 3JHH = 7.4 Hz, 2H, SCH2),
1.54 (m, 4H, SCH2CH2, CH2CH2OH), 1.27 (m, 14H,
SCH2CH2(CH2)7CH2CH2OH), ꢀ12.53 (s, 1H, OsHOs), ꢀ17.40 (s, 1H,
OsHOs)
12b
2108w, 2068vs, 2058m, 2020s, 1996w,
1982w
1906 (1905)
15b
17b
18b
21b
2114w, 2110w, 2076m, 2070s, 2066m,
2061m, 2027vs, 2017m, 2003w, 1991w,
1986w
2112w, 2109w, 2072s, 2067vs, 2063s,
2058m, 2029vs, 2023vs, 2014s, 2000m,
1989m, 1985w
2113w, 2109w, 2075s, 2067vs, 2063s,
2058m, 2028vs, 2024vs, 2014s, 1999m,
1989m, 1984w
1856 (1857)
1919 (1920)
1990 (1990)
1904 (1902)
7.58 (d, 1H, Ph), 7.56 (s, 1H, Ph), 7.47 (d, 1H, Ph), 7.21 (m, 1H, Ph),
ꢀ10.28 (s, 1H, OsHOs), ꢀ17.08 (s, 1H, OsHOs)
3
3
2.35 (t, JHH = 8.3 Hz, 2H, SCH2), 2.18 (t, JHH = 7.4 Hz, 2H,
CH2COOH), 1.61 (m, 4H, SCH2CH2, CH2CH2COOH), 1.24 (m, 22H,
SCH2CH2(CH2)11), ꢀ10.51 (s, 1H, OsHOs), ꢀ17.41 (s, 1H, OsHOs)
3
3
2.35 (t, JHH = 6.6 Hz, 2H, SCH2), 2.18 (t, JHH = 8.3 Hz, 2H,
CH2COOH), 1.54 (m, 4H, SCH2CH2, CH2CH2COOH), 1.24 (m, 22H,
SCH2CH2(CH2)11), ꢀ10.51 (s, 1H, OsHOs), ꢀ17.41 (s, 1H, OsHOs)
3
2109w, 2069vs, 2059m, 2021s, 1997w
3.51 (t, JHH = 7.4 Hz, 4H, CH2O), 1.47 (m, 4H, HOCH2CH2), 1.22
(m, 16H, HOCH2CH2(CH2)8), ꢀ12.53 (s, 1H, OsHOs)
Table 4
Spectroscopic and analytical data for the ruthenium clusters
Compound IR (CH2Cl2) mCO
(cmꢀ1
FAB (m/z)
[M+]: Calc.
(Found)
1H d (ppm in CDCl3)
Elemental Anal. (%)
Calc. (Found)
)
3
14a(Ru)
15a(Ru)
2105w, 2066s,
2057m, 2024s,
2010w, 1992w
2107w, 2068s,
2058m, 2022vs,
1962w
2106w, 2067s,
2057m, 2024s, 2015w
2104w, 2064vs,
2053m, 2022s, 2005w
689 (685)
3.13 (t, JHH = 6.6 Hz, 2H, CH2), 2.95 (t, 2H, CH2), ꢀ15.42 (s, 1H,
RuHRu)
3
3
738 (737)
8.0 (s, 1H, Ph), 7.94 (d, JHH = 7.4 Hz, 1H, Ph), 7.59 (d, JHH = 6.6 Hz,
1H, Ph), 7.35 (t, JHH = 7.4 Hz, 1H, Ph), ꢀ14.96 (s, 1H, RuHRu)
3
3
16a(Ru)
17a(Ru)
738 (663)
802 (799)
8.08 (d, 2H, Ph), 7.47 (d, JHH = 8.1 Hz, 2H, Ph), ꢀ15.08 (s, 1H,
RuHRu)
2.34 (t, 3JHH = 7.4 Hz, 2H, CH2COOH), 2.14 (t, 2H, SCH2), 1.62 (m, 4H, C, 31.46 (31.84); H,
SCH2CH2, CH2CH2COOH), 1.28 (m, 12H,
2.77 (3.19); S, 4.00
(4.29)
C, 35.82 (36.07); H,
3.70 (3.57); S, 3.68
(3.57)
SCH2CH2(CH2)6CH2CH2COOH), ꢀ15.36 (s, 1H, RuHRu)
3
3
18a(Ru)
2104w, 2063vs,
2055m, 2021s,
2006w, 1988w
872 (873)
2.34 (t, JHH = 7.4 Hz, 2H, CH2COOH), 2.14 (t, JHH = 8.3 Hz, 2H,
SCH2), 1.64 (m, 4H, SCH2CH2, CH2CH2COOH), 1.25 (m, 22H,
SCH2CH2(CH2)11CH2CH2COOH), ꢀ15.36 (s, 1H, RuHRu)
Analyzer. The clusters [Os3(CO)10(l-H)(l-OH)], 1, and
[Os3(CO)10(NCCH3)2], 2, were prepared according to
reported procedures [11,12]. [Os3(CO)12], 3a, and
[Ru3(CO)12], 3b, were purchased from Oxkem Ltd., and
all other reagents were purchased from other commercial
sources, and used as supplied without further purification.
NMR spectroscopy. With cluster 2 (80 mg, 0.085 mmol),
the mixture with excess ligand in dichloromethane (30 ml)
was allowed to stir at ambient temperature overnight. After
the reaction, the solvents were removed in vacuo and the
products purified by column chromatography using
hexane/DCM as the eluant; the type B clusters were eluted
first. With cluster 3b (30 mg), the mixture with a stoichiom-
etric amount of ligand in toluene (10 ml) was heated at
60 °C for 1 h. After the reaction, the solvents were
removed in vacuo and the products purified by column
chromatography using dichloromethane as the eluant.
Tables 2–4 contain the spectroscopic and analytical data
of the products.
4.2. Synthesis of clusters
In a typical experiment, to a solution of 1 (30 mg,
0.035 mmol) in toluene (20 ml) was added the ligand in
excess and HBF4/ether (one drop) and the resulting
mixture refluxed for 5 h. The reaction was monitored by

1298
C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
Table 5
Crystal and refinement data for 5a, 5b, 9a, 13a
Compound
5a
5b
9a
13a
Empirical formula
Formula weight
Crystal system
Space group
C16H6O10Os3S2
992.93
Triclinic
C26H6O20Os6S2
1843.63
Monoclinic
C2/c
33.388(2)
8.9768(6)
13.1874(9)
90
110.932(2)
90
3691.7(4)
4
3.317
20.762
3240
C12H6O11Os3S
928.83
Monoclinic
P21/n
8.7589(7)
13.3493(11)
32.146(3)
90
95.157(2)
90
3743.4(5)
8
3.296
20.480
3280
C12H4O12Os3S
942.81
Monoclinic
P21/n
9.4313(3)
17.0659(5)
11.9575(4)
90
105.544(2)
90
1854.21(10)
4
3.377
20.680
1664
ꢀ
P1
˚
a (A)
9.1515(3)
9.3399(3)
˚
b (A)
˚
c (A)
14.6987(5)
80.5880(10)
86.0230(10)
63.6290(10)
1110.46(6)
2
2.970
17.358
884
a (°)
b (°)
c (°)
3
˚
Volume (A )
Z
Dcalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
Crystal size (mm)
h Range for data collection (°)
0.32 ꢁ 0.20 ꢁ 0.06
2.46–30.50
16,621
0.20 ꢁ 0.12 ꢁ 0.02
2.36–29.97
16,837
0.36 ꢁ 0.24 ꢁ 0.16
2.36–29.99
24,188
0.36 ꢁ 0.22 ꢁ 0.12
2.13–28.27
17,223
Reflections collected
Independent reflections [Rint
]
6254 [0.0263]
0.4223 and 0.0720
6254/0/281
1.070
5224 [0.0421]
0.6815 and 0.1035
5224/0/249
1.134
10,408 [0.0367]
0.1381 and 0.0508
10,408/0/493
1.021
4594 [0.0455]
0.1904 and 0.0502
4594/0/265
1.043
Maximum and minimum transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R1 = 0.0239,
wR2 = 0.0589
R1 = 0.0267,
wR2 = 0.0601
2.036 and ꢀ1.300
R1 = 0.0396,
wR2 = 0.0802
R1 = 0.0480,
wR2 = 0.0842
2.050 and ꢀ1.453
R1 = 0.0327,
wR2 = 0.0651
R1 = 0.0458,
wR2 = 0.0686
1.263 and ꢀ2.209
R1 = 0.0319,
wR2 = 0.0707
R1 = 0.0400,
wR2 = 0.0738
1.490 and ꢀ1.574
R indices (all data)
Largest difference in peak and hole
ꢀ3
˚
(e A
)
Table 6
Crystal and refinement data for 14a, 15a, 15b and 8
Compound
14a
15a
15b
8
Empirical formula
Formula weight
Crystal system
Space group
C
956.84
Triclinic
13H6O12Os3S
C17H6O12Os3S
1004.88
Orthorhombic
Pbca
C27H6O22Os6S
1855.58
Tetragonal
I41/a
23.727(3)
23.727(3)
26.730(8)
90
90
90
15049(6)
16
3.276
C21H2N2O19Os6S3
1823.63
Orthorhombic
P212121
10.8843(6)
11.6681(7)
27.8651(16)
90
90
90
3538.8(4)
4
3.423
ꢀ
P1
˚
a (A)
9.0749(3)
12.3476(5)
12.9906(5)
28.1609(12)
90
90
90
4517.1(3)
8
2.955
16.988
3584
˚
b (A)
14.6717(5)
39.0412(12)
91.9960(10)
90.9060(10)
91.3260(10)
5192.8(3)
10
3.060
18.463
4240
˚
c (A)
a (°)
b (°)
c (°)
3
˚
Volume (A )
Z
Dcalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
20.324
13,056
21.713
3192
Crystal size (mm)
h Range for data collection (°)
Reflections collected
0.22 ꢁ 0.10 ꢁ 0.05
2.06–26.37
71,185
0.36 ꢁ 0.30 ꢁ 0.14
2.19–26.3
41,930
0.22 ꢁ 0.12 ꢁ 0.07
2.06–26.37
72,144
0.18 ꢁ 0.08 ꢁ 0.06
2.01–26.02
49,350
Independent reflections [Rint
]
21,250 [0.0642]
0.4587 and 0.1063
21250/0/1306
1.031
4619 [0.0638]
0.1995 and 0.0639
4619/0/321
1.040
7688 [0.0927]
0.3304 and 0.0944
7688/0/508
1.121
6981 [0.0768]
0.3558 and 0.1115
6981/126/460
1.133
Maximum and minimum transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R1 = 0.0464,
wR2 = 0.0885
R1 = 0.0666,
wR2 = 0.0967
–
R1 = 0.0274,
wR2 = 0.0625
R1 = 0.0333,
wR2 = 0.0649
–
R1 = 0.0411,
wR2 = 0.0878
R1 = 0.0512,
wR2 = 0.0915
–
R1 = 0.0471,
wR2 = 0.1004
R1 = 0.0532,
wR2 = 0.1027
0.000(19)
2.947 and ꢀ1.261
R indices (all data)
Absolute structure parameter
Largest difference in peak and hole
1.792 and ꢀ1.217
2.017 and ꢀ0.803
2.330 and ꢀ1.155
ꢀ3
˚
(e A
)

C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
1299
4.3. Reaction of 14a with 2
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2008.01.025.
A mixture of 14a (30 mg, 0.031 mmol) and 2 (29 mg,
0.031 mmol) in CHCl3 was stirred overnight at room
temperature. The solvent was then removed in vacuo and
separation of the residue by column chromatography using
hexane/CHCl3 as the eluant afforded [Os3(CO)10(l-H)-
(l,l-SCH2CH2COO)Os3(CO)10(l-H)], 14b (10.2 mg, 18.2%)
and unreacted 14a (19.4 mg).
References
14b: 1H NMR (CDCl3)d 2.49 (t, 2H, CH2O), 2.37 (t, 2H,
CH2S), ꢀ10.47 (s, OsHOs), ꢀ17.50 (s, OsHOs) ppm. Lit.
[6a]: d 2.47 (t), 2.34 (t), ꢀ10.50 (s), ꢀ17.50 (s) ppm.
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4.4. Reaction of HSCH2CH2COOH with 2 equiv. of 2
A mixture of HSCH2CH2COOH (2.84 mg, 0.027 mmol)
and 2 (50 mg, 0.054 mmol) in CHCl3 was stirred overnight
at room temperature. Subsequent workup as above affor-
ded 14b (10.7 mg, 11.0%) and 14a (10.5 mg, 20.5%).
(g) J.J. Venter, M.A. Jeremy, J. Mol. Catal. 56 (1989) 117;
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Crystals of diffraction quality were grown either by cool-
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collected on a Bruker APEX diffractometer equipped with
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a
CCD detector, employing Mo Ka radiation
˚
(k = 0.71073 A), at 223 K with the SMART suite of programs
[13]. Data were processed and corrected for Lorentz and
polarisation effects with SAINT [14], and for absorption
effects with SADABS [15]. Structural solution and refinement
were carried out with the SHELXTL suite of programs [16].
Crystal and refinement data are summarised in Tables 5
and 6.
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The structures were solved by direct methods to locate
the heavy atoms, followed by difference maps for the light,
non-hydrogen atoms. All non-hydrogen atoms were gener-
ally given anisotropic displacement parameters in the final
model. Organic hydrogen atoms were placed in calculated
positions and refined with a riding model, except for 13a
(refined on coordinates with isotropic thermal parameter
(b) E.W. Ainscough, A.M. Brodie, R.K. Coll, A.J.K. Mair, J.M.
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Chem. 52 (1999) 801;
2
˚
fixed at 0.04 A ) and 15a (refined freely). The metal
hydrides were either located from low angle difference elec-
tron density maps, or placed in calculated positions using
XHYDEX [17]. They were refined freely (5b and 9a), refined
on coordinates with isotropic thermal parameter fixed at
(e) K.M. Hanif, E.K. Shariff, M.A. Mottalib, M.B. Hursthouse,
K.M.A. Malik, E. Rosenberg, Polyhedron 19 (2000) 1073.
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2103.
2
˚
0.04 A (13a and 15a) or with a riding model.
[8] We have earlier reported the syntheses of 9a and 17a: (a) K.H. Chan,
`
W.K. Leong, G. Jaouen, L. Leclercq, S. Top, A. Vessieres, J.
Organomet. Chem. 691 (2006) 9;
Acknowledgements
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1055.
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Waters, Inorg. Chim. Acta 214 (1993) 21;
This work was supported by an A*STAR Grant (Re-
search Grant No. 022 109 0061) and one of us (C.L.)
thanks the University for a Research Scholarship.
(b) E.W. Ainscough, A.M. Brodie, R.K. Coll, T.G. Kotch, A.J.
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Appendix A. Supplementary material
CCDC 662214, 662215, 662216, 662217, 662218,
662219, 662220 and 662221 contain the supplementary
[10] A.J. Deeming, R. Vassh, Polyhedron 13 (1994) 3285.

1300
C. Li, W.K. Leong / Journal of Organometallic Chemistry 693 (2008) 1292–1300
[11] D. Roberto, E. Lucenti, C. Roveda, R. Ugo, Organometallics 16
[15] G.M. Sheldrick, SADABS, 1996.
(1997) 5974.
[16] SHELXTL Version 5.1, Bruker AXS Inc., Madison, Wisconsin, USA,
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1997.
[13] SMART Version 5.628, Bruker AXS Inc., Madison, Wisconsin, USA,
[17] A.G. Orpen, XHYDEX: A Program for Locating Hydrides in Metal
Complexes, School of Chemistry, University of Bristol, UK,
1997.
2001.
[14] SAINT+ Version 6.22a, Bruker AXS Inc., Madison, Wisconsin, USA,
2001.