Triruthenium clusters containing mono and bidentate phosphines: Synthesis, structure, thermal reactivity and fluxional behavior

Article abstract of DOI:10.1016/j.jics.2021.100023

The syntheses, structures and thermal reactions of [Ru₃(CO)₉{P(C₄H₃E)₃}(μ-dppe)] (2, E = S; 3, E = O; dppe = 1,2-bis(diphenylphosphino)ethane) are described. These triphosphine-substituted clusters ca

Full text of DOI:10.1016/j.jics.2021.100023

Journal of the Indian Chemical Society 98 (2021) 100023
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Triruthenium clusters containing mono and bidentate phosphines:
Synthesis, structure, thermal reactivity and fluxional behavior
Partha S. Roy, Md. Abdullah A. Mamun, Roknuzzaman, Shishir Ghosh **, Shariff E. Kabir *
Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
A R T I C L E I N F O
A B S T R A C T
Keywords:
Ruthenium
Carbonyl
1,2-bis(diphenylphosphino)ethane
tri(2-thienyl)phosphine
tri(2-furyl)phosphine
Fluxional behavior
X-ray structures
The syntheses, structures and thermal reactions of [Ru3(CO)9{P(C4H3E)3}(
μ-dppe)] (2, E ¼ S; 3, E ¼ O;
dppe ¼ 1,2-bis(diphenylphosphino)ethane) are described. These triphosphine-substituted clusters can be easily
obtained in high yield from the Me3NO initiated room temperature reaction between [Ru3(CO)10 -dppe)] (1)
(
μ
and P(C4H3E)3. Both clusters have been structurally characterized which reveals that the functionalized phos-
phine P(C4H3E)3 is coordinated to the remote ruthenium atom using the phosphorus atom, while the NMR
spectroscopic data indicate that both clusters are fluxional in solution mainly due to the ring-flipping process
involving the dppe ligand which has been probed by VT NMR spectroscopy. Thermolysis of 2 at 66 ꢀC affords 1 via
P(C4H3S)3 dissociation, whilst that of 3 under similar experimental conditions also furnishes the diruthenium
σ,π-furyl complex [Ru2(CO)6(μ, μ-P(C4H3O)2] (4) in addition to 1.
η2-C4H3O){
1. Introduction
upon mild heating (Scheme 1) [7], thus allowing their chemistry to be
explored. In contrast, the triruthenium complexes [Ru3(CO)9{P(-
The chemistry of functionalized phosphines such as tri(2-thienyl)
phosphine and tri(2-furyl)phosphine (Chart 1) is subject of
C4H3E)3}(μ
-dppf)], that contain a more flexible 1,10-bis(diphenylphos-
a
phino)ferrocene (dppf) instead of relatively rigid dppm, do not undergo
any discernible change upon mild heating. However, the dppf complexes
slowly undergo thermal rearrangement only at 80 ꢀC to afford the cyclo-
metalated clusters [HRu3(CO)7{μ3-(EH2C4)P(C4H3E)2}(μ-dppf)] (Scheme
1) [9]. These observations clearly indicate that the thermal rearrangement
of this type of triphosphine-substituted clusters, [Ru3(CO)9{P(-
C4H3E)3}(μ-diphosphine)], is influenced by the flexibility of the diphos-
phine backbone. In order to further explore this area, we have now
synthesized the triruthenium 1,2-bis(diphenylphosphino)ethane (dppe)
continuing interest due to their importance in transition metal catalysis
[1–3], since catalysts employing these ligands are often more active than
traditional triphenylphosphine based catalysts [1,2]. In addition, the
chemistry of phosphine ligands containing pyrrolyl and thienyl sub-
stituents has been widely studied because of their respective importance
in the hydrodenitrogenation [4] and hydrodesulfurization [5] processes,
and some recent developments reveal the intriguing reactivity patterns of
these phosphines towards metal carbonyl clusters [6].
In this context, we have been studying the coordination chemistry of
tri(2-theinyl)phosphine and tri(2-furyl)phosphine over the years [7–13]
which reveals that these phosphines are not only potential alternatives to
triphenylphosphine in a range of stoichiometric and catalytic trans-
formations [1,2], but may also function as a source of novel alkynyl de-
rivatives based on thiophyne (C4H2S) and furyne (C4H2O) platforms,
complexes [Ru3(CO)9{P(C4H3E)3}(μ-dppe)] (2, E ¼ S; 3, E ¼ O) and
investigated their thermal reactions the details of which are described in
this paper.
2. Experimental
which are generated as
a
result of both carbon-phosphorus and
2.1. Methods and materials
carbon-hydrogen bond activation [7,8]. For example, the triruthenium
bis(diphenylphosphino)methane (dppm) complexes [Ru3(CO)9{P(-
All reactions were carried out under a dry nitrogen atmosphere using
standard Schlenk techniques unless otherwise noted. Reagent grade
solvents were dried using appropriate drying agents and distilled prior to
C4H3E)3}(
clusters [HRu3(CO)7(
μ
-dppm)] convert cleanly to give the thiophyne and furyne
μ
3-C4H2E){ -P(C4H3E)2}( -dppm)] in good yield
μ
μ
* Corresponding author.
** Corresponding author.
E-mail addresses: sghosh_006@yahoo.com (S. Ghosh), skabir_ju@yahoo.com (S.E. Kabir).
https://doi.org/10.1016/j.jics.2021.100023
Received 28 November 2020; Received in revised form 7 January 2021; Accepted 5 March 2021
0019-4522/© 2021 Indian Chemical Society. Published by Elsevier B.V. All rights reserved.

P.S. Roy et al.
Journal of the Indian Chemical Society 98 (2021) 100023
Scheme 1. Thermal reactions of [Ru3(CO)9{P(C4H3E)3}(μ-diphosphine)] (E ¼ S, O; diphosphine ¼ dppm, dppf) [7,9].
use by standard methods. Infrared spectra were recorded on a Shimadzu
FTIR Prestige 21 spectrophotometer, and the 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 residual protons of the
Table 1
Crystal data and structure refinement details for compounds 2 and 3.
Compound
2
3
deuterated NMR solvent (1H) or external 85% H3PO4 31P), as appro-
(
CCDC
2045763
C47H33O9P3Ru3S3⋅C6H14
1320.20
150(1)
0.71073
2044529
4C47H33O12P3Ru3
4743.41
220(1)
0.71073
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell dimensions:
a (Å)
priate. Elemental analyses were performed by the Microanalytical Lab-
oratory of Wazed Miah Science Research Center at Jahangirnagar
University. [Ru3(CO)12] was purchased from Strem Chemical Inc. and
used without further purification. Tri(2-thienyl)phosphine [P(C4H3S)3],
tri(2-furyl)phosphine [P(C4H3O)3] and bis(diphenylphosphino)ethane
(dppe) were purchased from Acros Organics and used as received. The
Monoclinic
P21/n
Orthorhombic
Pbca
18.9980(3)
13.04878(16)
23.9536(4)
90
112.498(2)
90
14.670(3)
19.504(4)
38.050(8)
90
90
90
starting cluster [Ru3(CO)10(μ-dppe)] (1) was prepared according to a
b (Å)
c (Å)
published procedure [14]. All products reported herein were separated in
the air by TLC plates coated with 0.25 mm of silica gel (HF254-type 60, E.
Merck, Germany).
α
(ꢀ)
β (ꢀ)
γ (ꢀ)
Volume (Å3)
5486.21(17)
4
10887(4)
2
2.2. Reaction of [Ru3(CO)10
(μ-dppe)] (1) with P(C4H3S)3
Z
Density (calculated) (Mg/
1.598
1.447
m3)
[Ru3(CO)10 -dppe)] (1) (100 mg, 0.102 mmol) and P(C4H3S)3 (36 mg,
(
μ
Absorption coefficient
1.070
0.963
0.128 mmol) was dissolved in 20 mL CH2Cl2 in a three-neck round-bottom
flask with the aid of a magnetic stirrer. A freshly prepared CH2Cl2 solution
(15 mL) of Me3NO (8 mg, 0.107 mmol) was added dropwise to this solu-
tion. After the addition of Me3NO was completed, the reaction mixture was
further stirred at room temperature for 1 h. The solvent was then removed
under reduced pressure and the residue was recrystallised from n-hexane/
(mmꢁ1
)
F(000)
2648
4704
Crystal size (mm3)
2θ Range for data
collection (ꢀ)
0.18 ꢂ 0.18 ꢂ 0.15
0.18 ꢂ 0.09 ꢂ 0.06
5.304 to 58.97
5.104 to 54.454
Reflections collected
Independent reflections
93626
14104 [Rint ¼ 0.0311]
360459
12118 [Rint ¼ 0.0883]
CH2Cl2 at 4 ꢀC which afforded [Ru3(CO)9{P(C4H3S)3}(
(113 mg, 90%) as red crystals.
μ-dppe)] (2)
[Rint
]
Data/restraints/
parameters
Goodness-of-fit on F [2]
14104/0/642
12118/0/586
Data for 2: Anal. Calcd. for C47H33O9P3Ru3S3: C, 45.74; H, 2.70.
Found: C, 45.98; H, 2.81%. IR (νCO, CH2Cl2): 2051 m, 1995 vs, 1974 vs,
1937 sh, 1922 sh cmꢁ1. 1H NMR (CDCl3): δ 7.64 (m, 3H), 7.52 (m, 8H),
7.42 (m, 12H), 6.70 (m, 3H), 6.44 (m, 3H), 2.20 (m, 4H). 31P{1H} NMR
(CDCl3): δ 38.7 (d, J 22 Hz, 1P), 37.7 (s, 1P), ꢁ15.1 (d, J 22 Hz, 1P).
1.079
1.061
Final R indices [I > 2
σ
(I)]
R1 ¼ 0.0249,
wR2 ¼ 0.0514
R1 ¼ 0.0305,
wR2 ¼ 0.0538
0.63 and ꢁ0.64
R1 ¼ 0.0351,
wR2 ¼ 0.0910
R1 ¼ 0.0550,
wR2 ¼ 0.0996
0.57 and ꢁ0.56
R indices (all data)
Largest diff. peak and hole
(e. Åꢁ3
)
2.3. Reaction of [Ru3(CO)10(μ-dppe)] (1) with P(C4H3O)3
at 66 ꢀC for 3 h. The solvent was removed under reduced pressure and the
residue chromatographed by TLC on silica gel. Elution with cyclohexane/
CH2Cl2 (4:1, v/v) developed three bands. The first and second bands
afforded P(C4H3S)3 (trace) and [Ru3(CO)10(μ-dppe)] (1) (14 mg, 35%),
whilst the third was unconsumed 2 (6 mg).
A CH2Cl2 solution (15 mL) of Me3NO (8 mg, 0.107 mmol) was added
dropwise to a CH2Cl2 solution (20 mL) of [Ru3(CO)10 -dppe)] (1)
(μ
(100 mg, 0.102 mmol) and P(C4H3O)3 (30 mg, 0.129 mmol) and the re-
action mixture was stirred at room temperature for 1 h. The solvent was
then removed under vacuum and the residue recrystallised from n-hex-
ane/CH2Cl2 at 4 ꢀC which gave [Ru3(CO)9{P(C4H3O)3}(
(103 mg, 85%) as red crystals.
μ-dppe)] (3)
2.5. Thermolysis of [Ru3(CO)9{P(C4H3O)3}(μ-dppe)] (3)
Data for 3: Anal. Calcd. for C47H33O12P3Ru3: C, 47.60; H, 2.81. Found:
C, 47.93; H, 2.90%. IR (νCO, CH2Cl2): 2051 m, 1994 vs, 1973 vs, 1939 sh,
A thf solution (20 mL) of 3 (50 mg, 0.042 mmol) was heated to reflux
at 66 ꢀC for 3 h. The solvent was removed under vacuum and the residue
separated by TLC on silica gel. Elution with cyclohexane/CH2Cl2 (4:1, v/
v) developed three bands. The first band afforded the previously reported
1921 m cmꢁ1 1H NMR (CDCl3, 298K): δ 7.65 (m, 3H), 7.53 (br, s, 8H),
.
7.43 (br, s, 12H), 6.71 (m, 3H), 6.45 (m, 3H), 2.19 (m, 4H). 31P{1H} NMR
(CDCl3, 298 K): δ 39.1 (s, 1P), 38.1 (s, 1P), 14.6 (s, 1P). 1H NMR (CDCl3,
213 K): δ 7.77 (m, 4H), 7.66 (m, 3H), 7.55 (m, 6H), 7.36 (m, 6H), 7.25
(m, 4H), 6.75 (m, 3H), 6.47 (m, 3H), 2.58 (m, 2H) 2.74 (m, 2H). 31P{1H}
NMR (CDCl3, 213 K): δ 40.2 (s, 1P), 39.3 (s, 1P), 15.9 (s, 1P).
diruthenium compound [Ru2(CO)6(μ, μ-P(C4H3O)2] (4) [15]
η2-C4H3O){
(10 mg, 39%), while the second band yielded [Ru3(CO)10(μ-dppe)] (1)
(17 mg, 41%). The third band was unconsumed 3 (4 mg).
2.4. Thermolysis of [Ru3(CO)9{P(C4H3S)3}(
μ-dppe)] (2)
2.6. Crystal structure determination
A thf solution (20 mL) of 2 (50 mg, 0.041 mmol) was heated to reflux
Suitable single crystals of 2 and 3 were mounted on an Agilent Super
2

P.S. Roy et al.
Journal of the Indian Chemical Society 98 (2021) 100023
Scheme 2. Reactions of [Ru3(CO)10(μ-dppe)] (1) with P(C4H3S)3 and P(C4H3O)3.
Fig. 1. Molecular structures of [Ru3(CO)9{P(C4H3S)3}(μ-dppe)] (2) (left) and [Ru3(CO)9{P(C4H3O)3}(μ-dppe)] (3) (right) showing 50% probability atomic
displacement ellipsoids. Hydrogen atoms are omitted for clarity.
but we were able to refine it anisotropically and hydrogen atoms were
also included in it using a riding model. “Compound 2 shows a ‘Level B
checkCIF alert’ mainly due to omission of a large number of low-order
reflections from the (final) least-squares refinement.” Additional crys-
tallographic data are given in Table 1.
Table 2
Selected structural parameters for [Ru3(CO)9{P(C4H3S)3}(
μ
-dppe)] (2) and
[Ru3(CO)9{P(C4H3O)3}(
μ-dppe)] (3) (bond lengths in [Å] and bond angles in
[ꢀ]).
Compound
2
3
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(1)–P(1)
Ru(2)–P(2)
Ru(3)–P(3)
Ru(2)‒Ru(1)‒Ru(3)
Ru(1)‒Ru(2)‒Ru(3)
Ru(2)‒Ru(3)‒Ru(1)
P(1)‒Ru(1)‒Ru(2)
P(1)‒Ru(1)‒Ru(3)
P(2)‒Ru(2)‒Ru(1)
P(2)‒Ru(2)‒Ru(3)
P(3)‒Ru(3)‒Ru(1)
P(3)‒Ru(3)‒Ru(2)
2.8307(2)
2.8667(2)
2.8468(2)
2.3316(5)
2.3230(5)
2.3231(5)
59.953(5)
60.650(5)
59.397(5)
166.306(13)
116.986(13)
157.354(13)
100.144(12)
150.556(13)
98.496(13)
2.8754(7)
2.8315(6)
2.8789(6)
2.3061(10)
2.3451(10)
2.3167(9)
60.586(10)
58.953(13)
60.461(17)
106.90(2)
166.79(3)
158.85(2)
101.05(3)
162.43(2)
103.75(3)
3. Results and discussion
3.1. Reaction of [Ru3(CO)10
(
μ
-dppe)] (1) with P(C4H3E)3 (E ¼ S, O)
Room temperature reaction between [Ru3(CO)10 -dppe)] (1) and
(μ
P(C4H3E)3 in the presence of Me3NO led to the formation of
[Ru3(CO)9{P(C4H3E)3}(
μ
-dppe)] (2, E ¼ S; 3, E ¼ O) as red, air-stable
crystalline solid in ca. 90% yield, after usual chromatographic separa-
tion and workup (Scheme 2). Both new clusters have been characterized
by elemental and spectroscopic data in addition to single crystal X-ray
diffraction analyses.
ORTEP diagrams of the molecular structure of 2 and 3 are depicted in
Fig. 1 and selected bond lengths and angles are listed in Table 2. Both
molecules contain a triruthenium core ligated by nine carbonyls, a dppe
and a P(C4H3S)3 or P(C4H3O)3 ligands. The effect of P(C4H3E)3 substi-
tution on the Ru3-triangle is unremarkable, as the average Ru–Ru dis-
tance (2.8481 Å in 2 and 2.8619 Å in 3) being not significantly different
from that found for 1 (2.853 Å) [14] or even for [Ru3(CO)12] (2.851 Å)
[22]. The diphosphine (dppe) acts in bridging capacity and the
non-planarity of the resulted Ru–P–C–C–P–Ru ring, a feature also
observed in the parent cluster 1, is one of the main structural features of 2
and 3. In both clusters, all three phosphorus atoms occupy an equatorial
coordination site on each ruthenium atoms, and the average Ru–P bond
distance (2.3259 Å in 2 and 2.3226 Å in 3) are very similar to that
Nova dual diffractometer (Agilent Technologies Inc., Santa Clara, CA) or
on a Bruker D8 Venture diffractometer using a Nylon loop and Paratone
oil, and the diffraction data were collected at 150(1) K (for 2) or 220(1) K
(for 3) using Mo-K
α radiation (λ ¼ 0.71073). Unit cell determination,
data reduction, and absorption corrections for 2 were carried out using
CrysAlisPro [16]. Data reduction and integration for 3 were carried out
with SAINTþ [17] and absorption corrections were applied using the
program SADABS [18]. The structures were solved with the ShelXS [19]
structure solution program by direct methods and refined by full-matrix
least-squares on the basis of F2 using ShelXL [20] or XL [19] within the
OLEX2 [21] graphical user interface. Non-hydrogen atoms were refined
anisotropically and hydrogen atoms were included using a riding model.
The asymmetric unit of 2 also contains a disordered n-hexane molecule,
observed for related clusters such as [Ru3(CO)9{P(C4H3S)3}(
(2.3324 Å) [7] and [Ru3(CO)9{P(C4H3O)3}( -dppf)] (2.3375 Å) [9]. The
nine carbonyls are equally distributed between the three ruthenium
μ-dppm)]
μ
3

P.S. Roy et al.
Journal of the Indian Chemical Society 98 (2021) 100023
Scheme 3. Proposed ring-flipping process in 2 and 3.
Fig. 2. Variable-temperature 1H NMR spectra in the aliphatic region for 3 recorded over the temperature range 213–298 K.
plane but are screwed with respect to each other. This type of distortion is
common and also observed in the structure of the parent cluster 1 [14],
and even to a small extent in the structures of [M3(CO)12] (M ¼ Ru, Os)
[22,23].
The spectroscopic data indicate that both clusters are fluxional in
solution. At room temperature, the 1H NMR spectra of both clusters show
a multiplet in the aliphatic region (δ 2.20 for 2 and δ 2.19 for 3) for the
four methylene protons of the dppe ligand in addition to a series of
multiplets in the aromatic region for the phenyl and theinyl or furyl ring
protons. The appearance of the four methylene protons resonance as a
single multiplet can be attributed to the ring-flipping process involving
the dppe ligand as shown in Scheme 3, which was also reported for the
dppe-bridged triosmium complex [Os3(CO)10
(μ-dppe)] [24] and its
Chart 1. Chemical structures of tri(2-thienyl)phosphine and tri(2-
furyl)phosphine.
protonated derivative [Os3(CO)10 -H)( -dppe)][PF6] [24]. To confirm
(
μ
μ
this assumption, we have carried out a VT NMR experiment for 3 the
results of which is shown in Fig. 2. At 213 K, the methylene protons of the
dppe ligand indeed appear as two multiplets at δ 2.58 and 1.73 which
atoms, and are bound to the metal centers in terminal fashion. In both
clusters, the axial OC‒Ru‒CO directions are not perpendicular to the Ru3
Scheme 4. Phosphine migration between equatorial positions of the unique ruthenium atom of [Ru3(CO)9{P(C4H3E)3}(μ-diphosphine)] [7,9].
4

P.S. Roy et al.
Journal of the Indian Chemical Society 98 (2021) 100023
Scheme 5. Thermal reactions of [Ru3(CO)9{P(C4H3E)3}(μ-dppe)] (2, E ¼ S; 3, E ¼ O).
coalesce at about 253 K to give a broad singlet (δ 2.19) at 273 K. The 31
P
cleavage of the coordinated P(C4H3O)3 ligand is also isolated in addition
to 1 from the thermal reaction of 3 under similar experimental condi-
tions. The thermolytic behavior of 2 and 3 is in sharp contrast with those
observed for their dppm and dppf analogues [Ru3(CO)9{P(-
{1H} NMR spectrum of 2 displays two doublets at δ 38.7 and ꢁ15.1 (J
22 Hz) and a sharp singlet at δ 37.7 at room temperature due to the
phosphorus atoms of the dppe and P(C4H3S)3 ligands, respectively,
indicating that the P(C4H3S)3 ligand does not move between equatorial
positions of the unique ruthenium atom which is quite common for
C4H3E)3}(μ-dppm)] (E ¼ S, O) [7] and [Ru3(CO)9{P(C4H3O)3}(μ-dppf)]
(E ¼ S, O) [9], respectively (Scheme 1). Thus, the present study also
underscores the influence of flexibility of the diphosphine backbone on
the thermal rearrangement of triphosphine-substituted clusters of the
[Ru3(CO)9(PR3)(μ-diphosphine)] complexes [7,9,25]. For example, such
movement of P(C4H3E)3 ligand has also been reported for
[Ru3(CO)9{P(C4H3E)3}(
μ
-dppm)] (E ¼ S, O) [7] and [Ru3(CO)9{P(-
general formula [Ru3(CO)9{P(C4H3E)3}(μ-diphosphine)] (E ¼ S, O).
C4H3E)3}(
μ
-dppf)] (E ¼ S, O) [9] (Scheme 4). In contrast, the 31P{1H}
NMR spectrum of 3 displays three singlets at δ 39.1, 38.1 and 14.6 at
room temperature, and the spectrum does not show any discernible
change upon cooling to 213 K. This suggests that a second fluxional
process such as movement of the P(C4H3O)3 ligand between equatorial
positions of the unique ruthenium atom or a more complex fluxional
process is occurring in solution for 3.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
3.2. Thermolysis of [Ru3(CO)9{P(C4H3E)3}(
μ-dppe)]
Financial support from the Ministry of Science and Technology, the
Government of the People's Republic of Bangladesh (SG and SEK) is
acknowledged. We thank the Wazed Miah Science Research Center,
Jahangirnagar University, Bangladesh for providing some technical fa-
cilities required for this work. We also thank Prof. Derek A. Tocher for X-
ray structure analysis of 2.
We next examined the thermal stability of [Ru3(CO)9{P(C4H3E)3}(
μ-
dppe)] (2, E ¼ S; 3, E ¼ O) in order to study the rearrangement of the
coordinated P(C4H3E)3 ligand. Heating a CH2Cl2 solution of 2 at 40 ꢀC in
the presence of equimolar amount of Me3NO only led to unspecific
decomposition, but [Ru3(CO)10(μ-dppe)] (1) was isolated from the re-
action mixture when 2 was heated at 66 ꢀC in the absence of Me3NO
(Scheme 5). This indicates that decomposition of 2 upon heating is
triggered by loss of P(C4H3S)3 ligand, and the isolation of 1 from this
thermal reaction can be attributed to the CO capture by the putative 46-
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.jics.2021.100023.
electron cluster [Ru3(CO)9(
μ-dppe)] generated in situ upon phosphine
dissociation.
On the contrary, thermolysis of 3 at 66 ꢀC led to the isolation of the
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In summary, we have investigated the reactions of [Ru3(CO)10
dppe)] (1) with two functionalized phosphines P(C4H3S)3 and
P(C4H3O)3. Two new triruthenium clusters [Ru3(CO)9{P(C4H3E)3}(
dppe)] (2, E ¼ S; 3, E ¼ O) have been isolated in high yield from these
reactions and the molecular structure of each product established by X-
ray crystallography. Thermolysis of 2 at 66 ꢀC leads to the formation of 1
via P(C4H3S)3 dissociation with subsequent capture of a CO from the
(μ-
μ-
[9] Hossain MK, Rajbangshi S, Rahaman A, Chowdhury MAH, Siddiquee TA, Ghosh S,
Richmond MG, Nordlander E, Hogarth G, Kabir SE. J. Organomet. Chem. 2014;760:
231.
reaction mixture. In contrast, the diruthenium
σ,π-furyl complex
[Ru2(CO)6( -P(C4H3O)2] (4) [15] formed by C–P bond
μ,
η2-C4H3O){
μ
5

P.S. Roy et al.
Journal of the Indian Chemical Society 98 (2021) 100023
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6