Reactions of [Os3(CO)10(μ-H)2] and [Os3(CO)8{μ3-Ph2PCH2P(Ph)C6H4}(μ-H)] with pymS?SnPh3 (pymS = pyrimidine-2-thiolate): Synthesis and Structure of Triosmium Clusters Containing pymS Ligand

Article abstract of DOI:10.1007/s10870-020-00849-y

Abstract: Reactivity of pymS?SnPh₃ (pymS = pyrimidine-2-thiolate) towards two unsaturated triosmium clusters [Os₃(CO)₁₀(μ-H)₂] and [Os₃(CO)₈{μ₃-Ph₂PCH₂P(Ph)C₆H₄}(μ-H)] are investigated. Reaction of pymS?SnPh₃ with [Os₃(CO)₁₀(μ-H)₂] affords [Os₃(CO)₁₀(μ-pymS)(μ-H)] (1) and [Os₃(CO)₉(μ₃-pymS)(μ-H)] (2), while with [Os₃(CO)₈{μ₃-Ph₂PCH₂P(Ph)C₆H₄}(μ-H)] leads to the isolation of only [Os₃(CO)₈(μ-pymS)(μ-H)(μ-dppm)] (3). In both reactions, the products are formed via incorporation of the thiolate part (pymS) of pymS?SnPh₃ into the parent clusters through Sn?S bond cleavage. Clusters 1–3 have been characterized by a combination of analytical and spectroscopic data together with single crystal X-ray diffraction analysis. Graphic Abstract: Reactions of pymS?SnPh₃ with two unsaturated triosmium clusters have been investigated which resulted in the isolation and characterization of three triosmium clusters containing a pymS ligand.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-020-00849-y

Journal of Chemical Crystallography
https://doi.org/10.1007/s10870-020-00849-y
ORIGINAL PAPER
Reactions of [Os3(CO)10(μ‑H)2] and [Os3(CO)8{µ3‑Ph2PCH2P(Ph)C6H4}
(μ‑H)] with pymS‒SnPh3 (pymS = pyrimidine‑2‑thiolate): Synthesis
and Structure of Triosmium Clusters Containing pymS Ligand
Md Tuhinur R. Joy1 · Shishir Ghosh1 · Sharif E. Kabir1
Received: 11 October 2019 / Accepted: 7 July 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
Reactivity of pymS‒SnPh3 (pymS=pyrimidine-2-thiolate) towards two unsaturated triosmium clusters [Os3(CO)10(μ-H)2]
and [Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] are investigated. Reaction of pymS‒SnPh3 with [Os3(CO)10(μ-H)2] afords
[Os3(CO)10(µ-pymS)(µ-H)] (1) and [Os3(CO)9(µ3-pymS)(µ-H)] (2), while with [Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)]
leads to the isolation of only [Os3(CO)8(μ-pymS)(μ-H)(μ-dppm)] (3). In both reactions, the products are formed via incorpora-
tion of the thiolate part (pymS) of pymS‒SnPh3 into the parent clusters through Sn‒S bond cleavage. Clusters 1–3 have been
characterized by a combination of analytical and spectroscopic data together with single crystal X-ray difraction analysis.
Graphic Abstract
Reactions of pymS‒SnPh3 with two unsaturated triosmium clusters have been investigated which resulted in the isolation
and characterization of three triosmium clusters containing a pymS ligand.
Keywords Osmium · Carbonyls · Pyrimidine-2-thiolate · Tin-sulfur bond cleavage · Crystal structure
Introduction
biological relevance [14–17] and potential as precursor for
binary metal-sulfde materials employed in the semiconduc-
tor industry [18–21]. Consequently, the reactivity of these
heterocyclic thiols towards various transition metal centers
has been widely investigated [1–13, 22–41]. Recently, we
have initiated a research program in our laboratory with the
aim of incorporating tin or germanium into the coordination
sphere of transition metal clusters together with heterocy-
clic thiolate ligands since both tin [42–45] and germanium
[46–48] are widely used as modifers to control the reactivity
and selectivity of transition-metal catalysts. To achieve this
Over the past four decades, transition metal complexes con-
taining heterocyclic-thiolate ligands have drawn consider-
able attention owing to their structural diversity [1–13],
* Shishir Ghosh
sghosh_006@yahoo.com
* Sharif E. Kabir
skabir_ju@yahoo.com
1
Department of Chemistry, Jahangirnagar University, Savar,
Dhaka 1342, Bangladesh
Vol.:(0123456789)
1 3

Journal of Chemical Crystallography
in one step we have used ligands that possess both func-
tionalities such as pyS‒SnPh3 (py = pyridine-2-thiolate)
and pymS‒SnPh3 (pym = pyrimidine-2-thiolate) [49–51].
For example, the reaction of pyS‒SnPh3 with [Ru3(CO)12]
aforded diruthenium [Ru2(CO)6(SnPh3)2(μ-pyS)] as the
major product together with a small amount of tetraru-
thenium [Ru4(CO)12(SnPh3)(μ3-pyS)], while the reac-
tion with [Os3(CO)10(NCMe)2] yielded only triosmium
[Os3(CO)9(SnPh3)(μ3-pyS)] [51] (Scheme 1). Unsaturated
[Os3(CO)8{μ3-PPh2CH2P(Ph)C6H4}(μ-H)] also reacted
with pyS‒SnPh3 to give [Os3(CO)8(μ-pyS)(μ-dppm)
(μ-H)] and the Os-Sn bimetallic cluster [Os3(CO)7(SnPh3)
{μ-Ph2PCH2P(Ph)C6H4}(μ-pyS)(μ-H)] [51] (Scheme 2).
As part of our investigation on bimetallic Os–Sn clus-
ters containing heterocylic thiolate ligand(s), we have now
investigated the reactions of unsaturated [Os3(CO)10(μ-H)2]
and [Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] with pymS‒
SnPh3. Unfortunately, these reactions do not furnish any
bimetallic Os–Sn clusters, but lead to the isolation of prod-
ucts formed via incorporation of only the heterocyclic thi-
olato part of the ligand into these clusters. The details of
these reactions are described in this article.
Experimental Section
Materials and Methods
Unless otherwise noted, all reactions were carried out under
a nitrogen atmosphere using standard Schlenk techniques.
Reagent grade solvents were dried by the standard meth-
ods and were freshly distilled prior to use. [Os3(CO)12] was
purchased from Strem Chemicals, Inc. and used without fur-
ther purifcation. Bis(diphenylphosphino)methane (dppm),
pyrimidine-2-thiol (pymSH) and triphenyltin chloride
(Ph3SnCl) were purchased from Sigma-Aldrich and used as
received. The precursor compounds [Os3(CO)10(μ-H)2] [52],
[Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] [53] and pymS‒
SnPh3 [54, 55] were prepared according to the literature.
Infrared spectra were recorded on a Shimadzu IR Prestige-21
spectrophotometer, while NMR spectra were recorded on a
Bruker Avance III HD (400 MHz) instrument. All chemical
shifts are reported in δ units and are referenced to the resid-
ual protons of the deuterated solvents (1H) and to external
85% H3PO4 (31P). Elemental analyses were performed by the
Microanalytical Laboratories of the Wazed Miah Science
Research Centre at Jahangirnagar University. Products were
Scheme 1 Reactions of
[Os3(CO)10(NCMe)2] and
[Ru3(CO)12] with pyS‒SnPh3
N
S
[Os3(CO)10(NCMe)2]
SnPh3
(OC)3 Os
Os (CO)3
80 o
C
S
N
Os
(CO)3
Ph3Sn
80 o
C
N
[Ru3(CO)12
]
N
N
S
OC
S
OC
SnPh3
CO
Ru
Ru (CO)3
Ru
+
Ru
Ru
Ph3Sn
OC
Ru
(CO)3
(CO)4
Ph3Sn
S
CO
CO
N
Ph
Ph
P
P
S
SnPh3
(CO)2
(OC)2
Os
H
N
S
PPh2
Ph3Sn
(CO)3
(OC)3Os
Os (CO)3
(OC)3Os
Os
+
Os
P
H
110 o
C
P
N
H
Os
Os
S
Ph
Os
(CO)3
P
Ph
(CO)2
(CO)2
Ph2
Ph
Ph
Scheme 2 Reaction of [Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] with pyS‒SnPh3
1 3

Journal of Chemical Crystallography
separated in the air by TLC plates coated with 0.25 mm of
silica gel (HF254-type 60, E. Merck, Germany).
C6H4}(μ-H)] (trace), while the fourth band afforded
[Os3(CO)8(μ-pymS)(μ-H)(μ-dppm)] (3) (17 mg, 31%) iso-
lated as yellow crystals after recrystallization from n-hexane/
CH2Cl2 at 4 ºC. The content of the frst and second bands
was too small for complete characterization.
Reaction of [Os3(CO10(µ‑H)2] with pymS‒SnPh3
To a CH2Cl2 solution (15 ml) of [Os3(CO)10(μ-H)2] (50 mg,
0.059 mmol) was added pymS‒SnPh3 (27 mg, 0.059 mmol)
and the reaction mixture was stirred at room temperature
for 24 h. The solvent was removed under reduced pres-
sure and the resulting residue chromatographed by TLC
on silica gel. Elution with cyclohexane/CH2Cl2 (7:3 v/v)
developed three bands. The first band was unreacted
[Os3(CO)10(μ-H)2] (trace), while the second and third bands
aforded [Os3(CO)10(µ-pymS)(µ-H)] (1) (25 mg, 44%) iso-
lated as yellow crystals and [Os3(CO)9(µ3-pymS)(µ-H)] (2)
(19 mg, 35%) isolated as red crystals, respectively, after
recrystallization from n-hexane/CH2Cl2 at 4 ºC.
Data for 3: Anal. Calc. for C37H26N2O8Os3P2S: C, 34.41;
H, 2.03; N, 2.17. Found: C, 34.75; H, 2.11; N, 2.23%. IR
(ν(CO), CH2Cl2): 2071 s, 2025 s, 1996 vs, 1955 w, 1927
w cm−1. 1H NMR (CDCl3): δ 8.54 (d, J 4.8 Hz, 1H), 7.72
(m, 2H), 7.56 (d, J 2.4 Hz, 4H), 7.48 (m, 7H), 7.37 (m, 4H),
7.31(m, 2H), 7.16 (m, 2H), 6.99 (t, J 4.8 Hz, 1H), 5.97 (m,
1H), 4.38 (m, 1H),−16.01 (d, J 30.4 Hz, 1H). 31P{1H} NMR
(CDCl3): δ−25.2 (d, J 44 Hz, 1P),−26.8 (d, J 44 Hz, 1P).
Crystal Structure Determination
Single crystals of 1–3 suitable for X-ray difraction analyses
were grown by slow difusion of n-hexane into a CH2Cl2
solution of each compound at 4 ºC. Crystals were mounted
on a nylon loop and difraction data collected on a Bruker
APEX-III CCD difractometer at low temperatures (see
Table 1) using Mo-Kα radiation (λ=0.71073 Å). Unit cell
determination, data reduction and integration were carried
out with SAINT + [56], and absorption corrections were
applied using the program SADABS [57]. The structures
were solved with the ShelXS [58] structure solution program
by direct methods and refned by full-matrix least-squares
on the basis of F2 using ShelXL [59] within the OLEX2
[60] graphical user interface. All non-hydrogen atoms were
refned anisotropically and the hydrogen atoms (except for
the hydrides) were included using a riding model. Pertinent
crystallographic parameters are given in Table 1.
Data for 1 Anal. Calc. for C14H4N2O10Os3S: C, 17.46;
H, 0.42; N, 2.91. Found: C, 17.78; H, 0.48; N, 3.01%. IR
(ν(CO), hexane): 2110 w, 2070 vs, 2062 s, 2023 vs, 2018s,
2008 s, 1987 w cm−1. 1H NMR (CDCl3): δ 8.65 (d, J 4.8 Hz,
2H), 7.15 (t, J 4.8 Hz, 1H),−17.18 (s, 1H).
Data for 2 Anal. Calc. for C13H4N2O9Os3S: C, 16.70;
H, 0.43; N, 3.00. Found: C, 16.97; H, 0.47; N, 3.05%. IR
(ν(CO), CH2Cl2): 2087 w, 2058 vs, 2029 vs, 2000 m, 1950
w cm−1. 1H NMR (CDCl3): δ 9.23 (dd, J 4.8, 2.4 Hz, 1H),
8.55 (dd, J 4.8, 2.4 Hz, 1H), 7.15 (t, J 4.8 Hz, 1H),−15.03
(s, 1H).
Thermolysis of [Os3(CO)10(µ‑pymS)(µ‑H)] (1) at 128
ºC
An n-octane solution (10 mL) of 1 (20 mg, 0.021 mmol)
was heated to refux for 4 h. The solvent was removed under
reduced pressure and the residue chromatographed by
TLC on silica gel. Elution with cyclohexane/CH2Cl2 (7:3
v/v) developed three bands. The frst band was unreacted
1 (trace), while the third band aforded 2 (12 mg, 62%).
The content of the second band was too small for complete
characterization.
Results and Discussion
Reaction of [Os3(CO10(µ‑H)2] with pymS‒SnPh3
The room temperature reaction between [Os3(CO)10(μ-H)2]
and pymS‒SnPh3 led to the formation of two new tri-
osmium clusters [Os3(CO)10(µ-pymS)(µ-H)] (1) and
[Os3(CO)9(µ3-pymS)(µ-H)] (2) in 44 and 35% yield, respec-
tively, after usual chromatographic separation and workup
(Scheme 3). Both 1 and 2 are formed by coordination of
pymS to the parent cluster via Sn‒S bond cleavage of
pymS‒SnPh3 with apparent elimination of Ph3SnH. For-
mation of 2 in this room temperature reaction is unexpected
since removal of a carbonyl from the remote osmium in
1 should require moderate heating under normal circum-
stances. In a separate experiment, we indeed found that 1
does not convert to 2 at room temperature, but requires heat-
ing in boiling n-octane (128 °C). This observation indicates
that 1 is not a precursor of 2 in this reaction, and they are
Reaction of [Os3(CO)8{µ3‑Ph2PCH2P(Ph)C6H4}(μ‑H)]
with pymS‒SnPh3
To
a
t o l u e n e s o l u t i o n ( 1 5 m L ) o f
[Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] (50 mg,
0.042 mmol) was added pymS‒SnPh3 (20 mg, 0.043 mmol)
and the reaction mixture was heated to refux for 1 h. The
reaction mixture was then allowed to cool to room tempera-
ture. The solvent was removed under reduced pressure and
the residue chromatographed by TLC on silica gel. Elution
with cyclohexane/CH2Cl2 (1:1, v/v) developed four bands.
The third band was unreacted [Os3(CO)8{µ3-Ph2PCH2P(Ph)
1 3

Journal of Chemical Crystallography
Table 1 Crystal data and structure refnement details for 1–3
Compound
1
2
3
CCDC
1,954,927
C21H6N3O15Os4.5S1.5
1444.28
193(1)
0.71073
1,954,928
C13H4N2O9Os3S
934.84
193(1)
0.71073
1,954,929
C37H26N2O8Os3P2S
1291.20
210(1)
0.71073
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell dimensions
a (Å)
Orthorhombic
Pnma
Monoclinic
P21/c
Monoclinic
P21
12.344(5)
8.971(4)
11.669(5)
b (Å)
c (Å)
37.421(14)
13.270(5)
11.710(5)
17.687(9)
28.103(10)
12.038(5)
α (°)
β (°)
90
90
90
6130(4)
90
90
93.031(18)
90
1855.4(15)
4
1855.4(15)
20.657
1648
0.151×0.101×0.078
4.546 to 54.352
− 11≤h≤11
− 14≤k≤15
− 22≤l≤22
23,138
106.671(13)
90
3782(3)
γ (°)
Volume (Å3)
Z
8
4
Density (calculated) (Mg/m3)
Absorption coefcient (mm−1
F(000)
3.130
18.766
5112
0.238×0.169×0.091
4.354 to 52.222
− 15≤h≤15
− 46≤k≤46
− 16≤l≤16
179,029
2.268
10.248
2400
0.354×0.113×0.043
4.57 to 56.806
− 15≤h≤15
− 37≤k≤37
− 15≤l≤16
73,199
)
Crystal size (mm3)
2θ range for data collection (°)
Index ranges
Refections collected
Independent refections [Rint]
Data/restraints/parameters
Goodness of ft on F2
6153 [Rint =0.0543]
6153/0/432
1.199
R1 =0.0189, wR2 =0.0355
R1 =0.0213, wR2 =0.0361
0.92 and − 1.82
4101 [Rint =0.0614]
4101/0/258
1.122
R1 =0.0208, wR2 =0.0476
R1 =0.0231, wR2 =0.0484
1.40 and − 1.65
18,825 [Rint =0.0321]
18,825/1/964
0.988
R1 =0.0229, wR2 =0.0316
R1 =0.0324, wR2 =0.0332
0.88 and − 0.71
Final R indices [I>2σ(I)]
R indices (all data)
Largest dif. peak and hole (e. Å−3
)
N
N
S
H
H
(OC)4Os
Os(CO)3
H
(OC)4Os
Os(CO)3
(OC)3Os
Os(CO)3
H
CH2Cl2
r. t.
N
+
+
N
S
Os
Os
Os
SnPh3
(CO)3
N
S
(CO)3
(CO)3
N
1
2
Scheme 3 Reaction of [Os3(CO)10(μ-H)2] with pymS‒SnPh3
formed following diferent pathways. We also assume that
the tin moiety of the ligand most probably plays a role in
facilitating the formation of 2 in this reaction. Both new
clusters have been characterized by elemental and spectro-
scopic data in addition to single crystal X-ray difraction
analyses.
The solid-state molecular structure of 1 is depicted in
Fig. 1 with the caption containing selected bond distances
and angles. The molecule contains an isosceles triangle of
osmium atoms [Os(1)–Os(2) 2.8623(9) Å, Os(1)–Os(3)
2.8637(10) Å and Os(2)–Os(3) 2.8381(8) Å] coordinated by
ten carbonyls, an edge bridging pymS ligand and a hydride.
1 3

Journal of Chemical Crystallography
Fig. 1 Molecular structure of [Os3(CO)10(μ-pymS)(μ-H)] (1) showing
50% probability atomic displacement ellipsoids. Pyrimidine ring hydro-
gen atoms are omitted for clarity. Selected bond lengths (Å) and bond
angles (°): Os(1)–Os(2) 2.8623(9), Os(1)–Os(3) 2.8637(10), Os(2)–
Os(3) 2.8381(8), Os(1)–S(1) 2.4094(15), Os(2)−S(1) 2.4211(13),
Os(2)−Os(1)–Os(3) 59.425(10), Os(1)–Os(2)–Os(3) 60.313(18),
Os(1)–Os(3)–Os(2) 60.26(3), S(1)–Os(1)–Os(2) 53.85(3), S(1)–Os(1)–
Os(3) 81.48(3), Os(1)–S(1)–Os(2) 72.68(3)
Fig. 2 Molecular structure of [Os3(CO)9(μ-pymS)(μ-H)] (2) show-
ing 50% probability atomic displacement ellipsoids. Pyrimidine
ring hydrogen atoms are omitted for clarity. Selected bond lengths
(Å) and bond angles (°): Os(1)–Os(2) 2.7953(9), Os(1)–Os(3)
2.8537(9), Os(2)–Os(3) 2.8012(13), Os(2)–N(1) 2.167(4), Os(1)–S(1)
2.4233(13), Os(3)–S(1) 2.4290(16), Os(2)–Os(1)–Os(3) 59.44(3),
Os(1)–Os(2)–Os(3) 61.316(15), Os(1)–Os(3)–Os(2) 59.240(17),
S(1)–Os(1)–Os(3) 54.07(4), S(1)–Os(1)–Os(2) 80.81(4), Os(1)–S(1)–
Os(3) 72.05(4), N(1)–Os(2)–Os(1) 88.35(10)
The pymS ligand bridges the Os(1)–Os(2) edge through
the sulfur atom and the Os–S bond distances [Os(1)–S(1)
2.4094(15) Å and Os(2)–S(1) 2.4211(13) Å] are similar to
those observed for related clusters [32–41, 51, 61–63]. The
hydride was located from the diference map and refned; it
was found to span across the same Os–Os edge bridged by
the pymS ligand. Both Os(1) and Os(2) are bound to three
carbonyls, while the remote osmium, Os(3) is coordinated
by four carbonyls. The gross structural features of 1 are akin
to those of its pyridine-2-thiolate (pyS) and 4,6-dimethylpy-
rimidine-2thiolate (Me2pymS) analogues [Os3(CO)10(µ-pyS)
(µ-H)] [61] and [Os3(CO)10(µ-Me2pymS)(µ-H)] [63], respec-
tively. The solution spectroscopic data of 1 are consistent
with the solid-state structure. The IR spectrum exhibits sev-
eral absorption bands between 2110 and 1987 cm−1 indicat-
ing the presence of only terminal carbonyls in the molecule,
through the sulfur atom, while coordinating to the third
osmium using one of the ring nitrogen atoms. The Os–N
[Os(2)–N(1) 2.167(4) Å] and Os–S [Os(1)–S(1) 2.4233(13)
Å and Os(3)−S(1) 2.4290(16) Å] bond distances are very
similar to those found in related clusters [32–41, 51, 61–63].
The hydride ligand was located from the structural analysis,
which also bridges the longest Os–Os edge, but lies on the
opposite side of the metallic plane with respect to the pymS
ligand. The spectroscopic data of 2 suggest that the solid-
state structure persists in solution. The IR spectrum shows
fve absorption bands within the range 2110–1987 cm−1
1
for the nine terminal carbonyls, while the H NMR spec-
1
whilst the H NMR spectrum displays a doublet at δ 8.65
trum displays an upfeld singlet at δ−15.03 for the bridging
hydride together with two doublet of doublets and a triplet
at δ 9.23 (J 4.8, 2.4 Hz), 8.55 (J 4.8, 2.4 Hz) and 7.15 (J
4.8 Hz), respectively, for the pyrimidine ring protons which
are in accord with the solid-state structure.
and a triplet at δ 7.15 (J 4.8 Hz) with an intensity ratio of 2:1
due to the pyrimidine ring protons together with an upfeld
singlet at δ−17.18 for the edge bridging hydride.
Figure 2 shows the solid-state molecular structure of
2 and its caption contains selected bond distances and
angles. The cluster core consists of an isosceles triangle
of osmium atoms [Os(1)–Os(2) 2.7953(9) Å, Os(1)–Os(3)
2.8537(9) Å and Os(2)–Os(3) 2.8012(13) Å] which is ligated
by nine carbonyls, a capping pymS and an edge bridging
hydride. The carbonyls are evenly distributed between three
osmium atoms. The pymS ligand lies almost perpendicular
to the metallic plane by bridging the longest Os–Os edge
Reaction of [Os3(CO)8{µ3‑Ph2PCH2P(Ph)C6H4}(μ‑H)]
with pymS‒SnPh3
Unlike [Os3(CO)10(μ-H)2], the unsaturated
[Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] did not react
with pymS‒SnPh3 at room temperature and required heat-
ing in boiling toluene, which resulted in the formation
1 3

Journal of Chemical Crystallography
of [Os3(CO)8(μ-pymS)(μ-H)(μ-dppm)] (3) in 31% yield
(Scheme 4). Cluster 3 is formed by incorporation of only
the heterocyclic thiolato part of the ligand and the tin
part is most probably eliminated as Ph3Sn(C6H4CH3) or
Ph3SnOH, since formation of 3 also requires an additional
hydrogen atom, which we assume is abstracted from the
solvent toluene molecule or adventitious water during the
reaction. In a separate experiment, we heated 3 in boil-
ing n-octane in order to coordinate one of the pyrimidine
ring nitrogen atoms to the cluster core, but we could not
isolate any product from this thermal reaction, which
only led to slow decomposition of 3. Cluster 3 was ear-
lier reported from the room temperature reaction between
[Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] and pyrimi-
dine-2-thiol (pymSH) and was characterized by analyti-
cal and spectroscopic data [64]. Now we have carried out
a single crystal X-ray difraction analysis for 3 the results
of which are summarized in Fig. 3.
The molecular structure of 3 is very similar to that
of its thiophenolate analog [Os3(CO)8(μ-SPh)(μ-H)
(μ-dppm)] [65]. The molecule comprises a triosmium
core with three slightly different Os–Os interactions
[Os(1)–Os(2) 2.8602(9) Å, Os(1)–Os(3) 2.8743(11) Å
and Os(2)–Os(3) 2.8494(9) Å]. Eight carbonyls, a dppm,
a pymS and a hydride complete the coordination sphere
of the cluster. The carbonyls are distributed in such a
way that both Os(1) and Os(2) are bonded to three, while
Os(3) is coordinated to two. The dppm ligand acts in
bridging capacity and spans the shortest Os–Os edge. The
pymS and hydride ligands bridge the longest Os–Os edge
simultaneously, lying on the opposite face of the metallic
plane with respect to each other. The Os–P [Os(2)–P(1)
2.3237(19) Å and Os(3)–P(1) 2.3150(18) Å] and Os − S
[Os(1)–S(1) 2.4041(18) Å and Os(3)–S(1) 2.4153(17)
Å] bond distances are very similar to those observed in
[Os3(CO)8(μ-SPh)(μ-H)(μ-dppm)] [65] and other related
clusters [32–41, 51, 61–63]. The solution spectroscopic
data of 3 are in accord with the solid-state structure. The
1H NMR spectrum displays an upfeld singlet at δ − 16.01
for the bridging hydride and two multiplets at δ 5.97 and
4.38, each integrating to one proton, attributed to the
methylene protons of the dppm ligand. The spectrum also
displays a series of multiplets in the aromatic region for
Fig. 3 Molecular structure of [Os3(CO)8(μ-pymS)(μ-H)(μ-dppm)]
(3) showing 50% probability atomic displacement ellipsoids. Hydro-
gen atoms except the bridging hydride ligand are omitted for clar-
ity. Selected bond lengths (Å) and bond angles (°): Os(1)–Os(2)
2.8602(9), Os(1)–Os(3) 2.8743(11), Os(2)–Os(3) 2.8494(9), Os(2)–
P(1) 2.3237(19), Os(3)–P(1) 2.3150(18), Os(1)–S(1) 2.4041(18),
Os(3)–S(1) 2.4153(17), Os(2)–Os(1)–Os(3) 59.59(3), Os(1)−Os(2)–
Os(3) 60.453(19), Os(1)–Os(3)–Os(2) 59.959(16), S(1)–Os(1)–Os(3)
53.57(4), S(1)−Os(1)–Os(2) 81.46(4), Os(1)–S(1)–Os(3) 73.23(5),
P(1)–Os(2)–Os(3) 92.53(4), P(1)−Os(2)–Os(3) 152.91(4)
the phenyl and pyrimidyl ring protons, whilst the 31P{1H}
NMR spectrum exhibits two equally intense doublets at
δ − 25.2 and − 26.8 (J 44 Hz) for the phosphorus atoms of
the dppm ligand.
Conclusions
The reactions of pymS‒SnPh3 with two unsatu-
rated triosmium clusters [Os3(CO)10(μ-H)2] and
[Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}(μ-H)] have been inves-
tigated which led to the isolation of two new triosmium clus-
ters [Os3(CO)10(µ-pymS)(µ-H)] (1) and [Os3(CO)9(µ3-pymS)
(µ-H)] (2) and the previously reported [Os3(CO)8(μ-pymS)
(μ-H)(μ-dppm)] [64]. These clusters are apparently formed
Scheme 4 Reaction of
N
Ph
[Os3(CO)8{µ3-Ph2PCH2P(Ph)
C6H4}(μ-H)] with pymS‒SnPh3
N
(OC)3Os
P
S
(CO)2
Os
PPh2
(OC)3Os
Os (CO)3
toluene
110 o
N
H
+
P
H
Os
SnPh3
C
Os
P
Ph
(CO)2
N
S
Ph2
(CO)3
Ph
3
1 3

Journal of Chemical Crystallography
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via Sn‒S bond cleavage of the pymS‒SnPh3 ligand fol-
lowed by incorporation of the heterocyclic thiolate moiety
into the parent clusters. The pymS ligand acts in edge bridg-
ing capacity in 1 and 3, while it caps a face of the metal
triangle in 2. The fate of the tin moiety remains unknown
from the present study. Although the reactions of ArS‒EPh3
(E=Sn, Ge) ligands with polynuclear transition metal cent-
ers usually aford products containing both thiolate and EPh3
moieties [51, 66], isolation of products containing only the
thiolate or EPh3 part from this type of reactions is rare but
not unprecedented [49, 50, 65]. For example, we have ear-
lier reported that a similar reaction between the unsaturated
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containing only the thiolate part of the ligand [65].
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Supplementary Data
Crystallographic data for the structural analyses have been
deposited with the Cambridge Crystallographic Data centre.
CCDC 1,954,927, CCDC 1,954,928 and CCDC 1,954,929
contain supplementary crystallographic data for compound
1, 2 and 3 respectively. These data can be obtained free of
charge from the Director, CCDC, 12 Union Road, Cam-
bridge, CB2 1 EZ, UK (fax: + 44-1223-336,033; Email:
deposit@ccdc.cam.ac.uk or www: https://www.ccdc.ac.uk).
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Acknowledgements Financial support from the Ministry of Science
and Technology, the Government of the People’s Republic of Bangla-
desh (SG and SEK) is acknowledged. We also thank the Wazed Miah
Science Research Center, Jahangirnagar University, Bangladesh for
providing some technical facilities required for this work.
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