Crystal structure characterization and catalytic application of novel route prepared Ru3(CO)9 DPAM (Diphenyl arsino methane)-tri phenyl phosphine derivatives

Article abstract of DOI:10.1080/15533174.2013.791839

Triruthenium dodecacarbonyl-Ru₃(CO)₁₂ based diphenylarsino methane-triphenyl phosphine derivatives, such as Ru ₃(CO)₉-dpam-tris (methyl phenyl) phosphine (1), Ru ₃(CO)₉-dpam-tris (methoxy p

Full text of DOI:10.1080/15533174.2013.791839

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:935–941, 2014
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.791839
Crystal Structure Characterization and Catalytic Application
of Novel Route Prepared Ru3(CO)9 DPAM (Diphenyl Arsino
Methane)-tri Phenyl Phosphine Derivatives
Omar Bin Shawakataly,1 R. Jothiramalingam,1,2 and I. A. Khan1
1 School of Distance Education, Chemical Science Division, Universiti Sains Malaysia, Penang, Malaysia
2 R & D Center, Department of Chemistry, VelTech Dr RR and Dr SR Technical University, Chennai, India
to Ru3(CO)10[Ph2P(CH2)2PPh2].[6] The previous study about
Triruthenium dodecacarbonyl-Ru3(CO)12 based dipheny-
larsino methane-triphenyl phosphine derivatives, such as
Ru3(CO)9-dpam-tris (methyl phenyl) phosphine (1), Ru3(CO)9-
dpam-tris (methoxy phenyl) phosphine (2), and Ru3(CO)9-dpam-
tris (fluro phenyl) phosphine (3) are synthesized by two step mod-
ified method. The catalytic hydrogenation of cyclohexene, styrene,
and phenyl acetylene, on above mentioned Ru-based organometal-
lic catalysts, has been studied under high pressure hydrogen at-
mosphere. The high pressure hydrogenation of cyclohexene and
phenyl acetylene on Complex (1–3), showed good catalytic activ-
ity under pressurized condition. Hydrogenation of cyclohexene on
Complex (3) showed better (50–65%) conversion in the presence
of toluene than hexane solvent. The effect of temperature, role of
solvent, and pressure conditions have also been studied.
mixed ligands was already conducted by using Rh complexes
of (diphenyl arsino diphenyl phosphino) methane.[7]
According to Sappa et al. (1972), the mono substituted tri-
nuclear compounds of Ru3(CO)9 μ3-x [where X = C2(t-Bu)
and C2(Ph)] show that the cluster is stable due to the pres-
ence of phenyl acetylene and tert-butyl group which has a
strong inductive effect.[8] Homo- and hetero-metallic ruthenium-
containing carbonyl clusters are proved as an efficient catalyst
for hydrogenation of alkynes[9] and of cyclic dienes.[10] The
structure-reactivity relationships have been studied and reaction
intermediates/by-products are isolated and characterized.[11] In
some instances, reaction mechanisms based on the nature of
the above derivatives have been proposed.[12] Ruthenium clus-
ter compounds have been used as catalyst precursors in sev-
eral catalytic reactions for example, carbonylation of alcohols,
isomerization, hydrogenation of olefins,[13–18] water gas shift
reaction,[19] and hydroformylation,[20] especially in homoge-
neous catalysis. Reactivity tests under conditions, where clus-
ter compounds might be expected to display catalytic activity,
would provide useful information of their structure and reactiv-
ity after the catalytic reactions. Usually under carbon monoxide
atmosphere, the simple metal carbonyl clusters tend to frag-
mentation to lower nuclearity carbonyl compound and in case
of hydrogen atmosphere causes the cluster formation. The be-
havior is more complicated in the case of both fragmentation
and formations of new hydride derivatives formation in pres-
ence of tri-metalic carbonyl complexes.[21] Hydrogenation of
phenyl acetylene and 3-phenylpropyne using Rh (diene) com-
plexes under homogeneous and heterogeneous condition was
reported.[22]
Keywords catalytic hydrogenation, cyclohexene, Ru3(CO)12, styrene
INTRODUCTION
Triruthenium dodecacarbonyl (Ru3(CO)12) is a cluster com-
pound that has an equilateral triangle of Ru atom with 12
terminal carbonyl groups, and it is a air-stable orange solid
which is soluble in most of the organic solvents.[1–3] The re-
activity of Ru3(CO)12 has been recognized for a long time
by its reaction towards halogens, thiols, phosphines, dienes,
etc.[4] The product of such a reaction with a ligand L is usu-
ally of the formula Ru3(CO)9L3.[3] The tri-substituted complex
is unreactive towards small molecules because of steric fac-
tor. The mixed-ligand cluster carbonyls with group 15 donor
ligands are unique because of their catalytic activity.[5] The
structure of Ru3(C26H24AsP)(CO)10 was synthesized using
Ru3(CO)12 with Ph2P(CH2)2AsPh2 ligand, which is similar
The present study deals with the structure and catalytic ac-
tivity of newly synthesized tri-Ru-dpam derivatives. Hydro-
genation of alkene (cyclohexene, styrene) and alkyene (phenyl
acetylene), under high pressure conditions, on the synthesized
complexes have been studied. The following three organometal-
lic complexes (1)–(3) are characterized by single crystal XRD,
and their catalytic properties were studied under high pressure
hydrogenation conditions.
Received 24 February 2013; accepted 27 March 2013.
Address correspondence to R. Jothiramalingam, R & D Center, De-
partment of Chemistry, VelTech Dr RR and Dr SR Technical University,
Chennai-600062, India. E-mail: rjothiram@gmail.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
935

936
O. B. SHAWAKATALY ET AL.
EXPERIMENTAL
Single Crystal X-ray Diffraction Study
Determination of cell constants and data collection were car-
ried out at 100.0(1) K, using the Oxford Cryosystem Cobra
low-temperature attachment with Mo Ka radiation (k = 0.71073
Å) on a Bruker SMART APEX2 CCD area-detector diffrac-
tometer equipped with a graphite monochromator. The struc-
ture was solved by direct methods and refined against F2 by
full-matrix least-squares, using SHELXTL.[23] Hydrogen atoms
were placed in calculated positions.
Synthesis of Complex 1
All manipulations were performed under a dry oxygen-
free dinitrogen atmosphere using standard Schlenk tech-
niques; all solvents were dried over sodium and dis-
tilled from sodium benzophenone ketyl under nitrogen. Tris
(4-methylphenyl) phosphine was used as ligand and μ-bis
(diphenylarsino) methane decacarbonyl triruthenium(0) (Bruce
et al., 1982) was prepared by two step route.[6] The title
compound was obtained by refluxing equimolar quantities of
Ru3(CO)10(μ-Ph2AsCH2AsPh2) (105.5 mg, 0.1 mmol) and tris
(4-methylphenyl) phosphine (30.4 mg, 0.1 mmol) in hexane un-
deranitrogenatmosphere. Crystalssuitablefor X-raydiffraction
were grown by slow solvent/solvent diffusion of CH3OH into
CH2Cl2.
FIG. 1a. ORTEP diagram of Complex (1).
hydrogen pressure maintained between 20–60 bar for differ-
ent conditions, temperature is fixed at 313 K for all reactions,
solvent effect (pentane and toluene) studied at fixed reaction
time of 5 hours. Conversion of the respective substrate was an-
alyzed by gas chromatography, using SPB non-polar capillary
column.
Synthesis of Complex 2
RESULTS AND DISCUSSION
All manipulations were performed under a dry oxygen-free
dinitrogen atmosphere using standard Schlenk techniques, un-
der nitrogen atmosphere. Tris (4-methylphenyl) phosphine was
used as ligand, and μ-bis (diphenylarsino) methane decacar-
bonyl triruthenium(0) was prepared by two step route.[25] The
title compound was obtained by refluxing equimolar quanti-
ties of Ru3(CO)10(μ-Ph2AsCH2AsPh2) (105.5 mg, 0.1 mmol)
and tris (4-methoxyphenyl) phosphine (32.23 mg, 0.1 mmol) in
hexane under a nitrogen atmosphere. Crystals suitable for X-
ray diffraction were grown by slow solvent/solvent diffusion of
CH3OH into CH2Cl2.
Single Crystal X-ray Diffraction Study of Complex (1)–(3)
Complex 1:
In the title triangulo-triruthenium compound, [Ru3(C25H22
As2)(C21H21P)(CO)9], the bis (diphenylarsino) methane ligand
bridges a Ru—Ru bond and the monodentate phosphine lig-
and bonds to the third Ru atom. Both the phosphine and arsine
ligands are equatorial with respect to the Ru3 triangle. Addition-
ally, each Ru atom carries one equatorial and two axial terminal
carbonyl ligands. The three phenyl rings of the phosphine make
Synthesis of Complex 3
Tris (4-flurophenyl) phosphine and bis (diphenylarsino)
methane (Strem chemicals) are used as received. Ru3(CO)10(μ-
Ph2AsCH2AsPh2) (105.5 mg, 0.1 mmol) and tris (4-flurophenyl)
phosphine (31.62 mg, 0.1 mmol) were refluxed for 15 minutes
in hexane (25 ml) under nitrogen atmosphere. Once the reaction
mixture turned into intense red colour, the solvent was removed
under vacuum. The reaction mixture was separated by TLC
(dichloromethane: hexane, 30:70). Two bands are appeared. The
major band (red) Rf = 0.56, yielded the title compound which
was crystallized from CH2Cl2—CH3OH.
Catalytic Activity Test
The stainless steel autoclave with inserted glass tube was
used as pressurized vessel to study the catalytic activity. The
FIG. 1b. Crystal packing structure diagram of Complex (1).

Ru3(CO)9 DPAM (DIPHENYL ARSINO METHANE)
937
dihedral angles of 86.89 (19)◦, 82.1 (2)◦, and 63.0 (2)◦ with
each other. The dihedral angles between the two phenyl rings
are 73.8 (2)◦ and 82.2 (3)◦, for the two diphenylarsino groups
(Fig. 1a). An intramolecular C H O hydrogen bond stabilizes
the molecular structure. In the crystal packing, molecules are
linked into chains down the b-axis via intermolecular C H O
hydrogen bonds.
The bond lengths and angles of title compound (Fig. 1a) are
comparable to those in related structures (Shawkataly et al.2006,
2009a).[24–26] The bis (diphenylarsino) methane ligand bridges
the Ru1 Ru2 bond and the monodentate phosphine ligand
bonds to the Ru3 atom. Both the phosphine and arsine ligands are
equatorial with respect to the Ru3 triangle. Additionally, each
Ru atom carries one equatorial and two axial terminal carbonyl
ligands. The three phosphine substituted phenyl rings make
dihedral angles (C26–C31/C32–C37, C26–C31/C38–C43, and
C32–C37/C38–C43) of 86.89 (19)◦, 82.1 (2)◦, and 63.0 (2)◦
with each other respectively. The dihedral angles between the
two phenyl rings (C1–C6/C7–C12 and C14–C19/C20–C25) are
73.8 (2)◦ and 82.2 (3)◦ for the two diphenylarsino groups respec-
tively. An intramolecular C27—H27A···O9 hydrogen bond sta-
bilizes the molecular structure. In the crystal packing (Fig. 1b),
the molecules are linked together into chains via intermolecular
C54—H54A···O2 hydrogen bonds along the b-axis (Fig. 1b).
FIG. 2a. ORTEP diagram of Complex (2).
benzene rings make dihedral angles (C26–C31/C32–C37,
C26–C31/C38–C43, and C32–C37/C38–C43) of 72.7 (3)◦, 80.9
(3)◦, and 70.8 (2)◦ with each other respectively. The dihedral
angles between the two benzene rings (C1–C6/C7–C12 and
C14–C19/C20–C25) are 79.9 (3)◦ and 81.5 (2)◦ for the two
diphenylarsino groups respectively. In the crystal structure, the
molecules are stacked along the b-axis (Fig. 2b).
Complex 2:
The asymmetric unit of the title triangulo-triruthenium com-
pound, Ru3(C25H22As2)(C20H19O2P)(CO)9] 0.15CH2Cl2, con-
tains one molecule of the triangulo-triruthenium complex and
one partially occupied dichloromethane solvent molecule. The
dichloromethane solvent lies across a crystallographic inversion
center, leading to the molecule being disordered over two po-
sitions of equal occupancy. The bis (diphenylarsino) methane
ligand bridges an Ru—Ru bond, and the monodentate arsine
ligand bonds to the third Ru atom. Both the arsine ligands are
equatorial with respect to the Ru3 triangle. In addition, each Ru
atom carries one equatorial and two axial terminal carbonyl lig-
ands. The three phosphorus bound benzene rings make dihedral
angles of 72.7 (3)◦, 80.9 (3)◦, and 70.8 (2)◦ with each other. The
dihedral angles between the two benzene rings are 79.9 (3)◦ and
81.5 (2)◦ for the two diphenyl arsino groups (Fig. 2a).
The asymmetric unit consists of one molecule of the
triangulo-triruthenium complex and a 15% partially occu-
pied molecule of dichloromethyl solvent (Fig. 2a). The
dichloromethyl solvent lies across a crystallographic inversion
center, leading to the molecule being disordered over two po-
sitions of equal occupancy. The bond lengths and angles of
title compound are comparable to those found in related struc-
ture (Shawkataly et al., 2009a).[24–26] The bis (diphenylarsino)
methane ligand bridges the Ru1—Ru2 bond and the monoden-
tate arsine ligand bonds to the Ru3 atom. Both the arsine
ligands are equatorial with respect to the Ru3 triangle. Ad-
ditionally, each Ru atom carries one equatorial and two ax-
ial terminal carbonyl ligands. The three phosphine-substituted
FIG. 2b. Crystal packing structure diagram of Complex (2).

938
O. B. SHAWAKATALY ET AL.
into a three dimensional framework. Intermolecular C—H—
interactions further stabilize the crystal structure.
The bond lengths and angles of the above compound
(Fig. 3a) are comparable to its related structures (Shawkataly
et al., 2006; Shawkataly et al., 2009a,b).[24–26] The bis (dipheny-
larsino) methane ligand bridges the Ru1—Ru2 bond and
TABLE 1
Unit cell parameters of as prepared three complexes
Complex 1
[Ru3(C25H22As2)
(C21H21P)(CO)9]
Mr = 1331.91
F(000) = 2632
Dx = 1.652 Mgm−3
Mo Kα radiation, λ =
0.71073 Å
Monoclinic, P21/c
Hall symbol: -P 2ybc
Cell parameters from
9940 reflections
θ = 2.3–26.0◦
FIG. 3a. ORTEP diagram of Complex (3).
a = 16.2585 (2) Å
b = 16.9247 (2) Å
c = 19.6900 (2) Å
β = 98.680 (1)◦ Plate, red
V = 5356.05 (11) Å3
Z = 4
Complex 3
μ = 2.15 mm−1
T = 296 K
In the title triangulo-triruthenium compound, [Ru3(C25H22-
(As2)(C18H12F3P)(CO)9], the bis(diphenylarsino) methane lig-
and bridges an Ru—Ru bond and the monodentate phosphine
ligand bonds to the third Ru atom. Both the phosphine and arsine
ligands are equatorial with respect to the Ru3 triangle. Addition-
ally, each Ru atom carries one equatorial and two axial terminal
carbonyl ligands. The three phosphine-substituted rings make
dihedral angles of 87.76 (13)◦, 57.43 (13)◦, and 73.81 (12)◦ with
each other. The dihedral angles between the pairs of rings are
69.78 (14)◦ and 83.38 (16)◦ for the two diphenylarsino groups
(Fig. 3a). In the crystal packing, molecules are linked by inter-
molecular C—H—F and C—H—O hydrogen bonds, forming
two-dimensional planes parallel to the ab plane. These planes
are also linked by intermolecular C—H—O hydrogen bonds
0.21 × 0.21 × 0.03 mm
Complex 2
[Ru3(C25H22As2)(C20H19O2P) F(000) = 2689
(CO)9]·0.15CH2Cl2
Mr = 1362.63
Dx = 1.594 Mgm−3
Mo Kα radiation, λ =
0.71073 Å
Monoclinic, P21/c
Hall symbol: -P 2ybc
Cell parameters from
9029 reflections
θ = 2.5–27.7◦
a = 13.3723 (4) Å
b = 16.9461 (6) Å
c = 25.0956 (8) Å
β = 93.293 (2)◦ Block, purple
V = 5677.5 (3) Å3
Z = 4
μ = 2.04 mm−1
T = 296 K
0.31 × 0.21 × 0.16 mm
Complex 3
[Ru3(C25H22As2)
(C18H12F3P)(CO)9]
Mr = 1343.81
F(000) = 2632
Dx = 1.748 Mgm−3
Mo Kα radiation, λ =
0.71073 Å
Monoclinic, P21/c
Hall symbol: -P 2ybc
Cell parameters from
9910 reflections
θ = 2.5–31.1◦
a = 16.3071 (2) Å
b = 16.8142 (2) Å
c = 18.8085 (2) Å
β = 98.105 (1)◦ Plate, red
V = 5105.6 (1) Å3
Z = 4
μ = 2.26 mm−1
T = 296 K
0.38 × 0.25 × 0.14 mm
FIG. 3b. Crystal packing structure diagram of Complex (3).

Ru3(CO)9 DPAM (DIPHENYL ARSINO METHANE)
939
TABLE 2
the monodentate phosphine ligand bonds to the Ru3 atom.
Both the phosphine and arsine ligands are equatorial with re-
spect to the Ru3 triangle. Additionally, each Ru atom carries
one equatorial and two axial terminal carbonyl ligands. The
three phosphine substituted phenyl rings (C26–C31, C32–C37,
and C38–C43) make dihedral angles (C26–C31/C32–C37,
C26–C31/C38–C43, and C32–C37/C38–C43) of 87.76 (13)◦,
57.43 (13)◦, and 73.81 (12)◦ with each other respectively. The
dihedral angles between the two phenyl rings (C1–C6/C7–C12
and C14–C19/C20–C25) are 69.78 (14)◦ and 83.38 (16)◦ for
the two diphenylarsino groups respectively. In the crystal
packing (Fig. 3b), the molecules are linked by intermolecu-
lar C23—H23A···F3 and C34—H34A···O3 hydrogen bonds to
form two-dimensional planes parallel to ab plane. These planes
are further linked by intermolecular C42—H42A···O2 hydro-
gen bonds into a three-dimensional framework. Intermolecular
C—H···π interactions further stabilize the crystal structure. The
unit cell parameters of as synthesized three complexes are shown
in Table 1.
Catalytic activity of complex (1)–(3) for high pressure
hydrogenation reactions
Substrate conversion (%)
Catalyst
Cyclohexene
Phenylacetylene
Styrene
Complex (1)
Complex (2)
Complex (3)
28
45
52
60
25
65
22
54
63
Reaction condition: substrate = 1 mL, solvent = 25 mL, catalyst =
2 mL (0.025g/50 mL toulene); pressure = 40bar; temperature = 313 K;
reaction time = 5h
functional methyl and methoxy groups connected to the aro-
matic ring. Complex (1) showed higher (60%) conversion for
phenyl acetylene and less conversion for cyclohexene. Complex
(2) showed the effective conversion for alkene substrate (cy-
clohexene and styrene) for hydrogenation compared to phenyl
acetylene conversion (Table 2). The functional group present in
the phosphene derivative, attached to the dodeco ruthenium car-
bonyl, is playing a crucial role via electron transfer mechanism
Catalytic Activity of Complex (1)–(3) for Hydrogenation
of Alkenes and Alkyne Under High Pressure Conditions
The catalytic hydrogenation activity of complexes (1)–(3) is in hydrogenation process of cyclic olefins and phenyl acety-
carried out under high pressure hydrogenated conditions. Pre- lene.[27] Figure 4 shows the bar diagram of catalytic hydrogena-
liminary test reactions were conducted using cyclohexene as tion of phenyl acetylene (PA) and styrene (ST) on complexes
model compound to study their hydrogenation activity by adopt- (1)–(3) at constant pressure. The trifluro phosphine derivative
ing suitable reaction conditions. Table 2 shows the catalytic hy- of tri ruthenium carbonyl complex (3) shows the effective cat-
drogenation of cyclohexene, phenyl acetylene, and styrene on alytic conversion towards hydrogenation reaction compared to
complexes (1)–(3) respectively. The complex (3) such as tri- complexes (2) and (3). The electron withdrawing nature of
fluro derivative of ruthenium dodecacorbnyl showed the better the fluorinated Ph3P-Ru3(CO)9 would weaken the cluster upon
(50–65%) activity towards hydrogenation of alkene and alkyne. hydrogenation and favor the fragment catalysis.[28] Whereas,
The complexes (1) and (2) show different activity to- complexes (1) and (2) show the vice versa effect on catalytic
ward phenyl acetylene and styrene hydrogenation due to their hydrogenation of PA and ST conversion with respect to the
FIG. 4. Cataytic hydrogeantion of Phenyl acetylene (PA) and Styrene (ST) on complexes (1)–(3) at 40 bar for 5 hour.

940
O. B. SHAWAKATALY ET AL.
activity of the cluster via increase in more hydrogen consump-
tion capacity. Figure 6 shows the PA and ST hydrogenation
activity on complex (3), at different pressure conditions. The flu-
orinated phosphine derivative of tri ruthenium cluster shows the
higher catalytic hydrogenation capacity for styrene with com-
plete selectivity towards ethyl benzene formation. The straight
forward fragmentation catalysis of complex (3) prefers to hy-
drogenate the C C double bond in styrene. Whereas, in the
case of phenyl acetylene hydrogenation occurred by oligomer-
ization of phenyl acetylene, results in hindering the higher cat-
alytic conversion. Hence, complex (3) showed slightly lesser
activity for phenyl acetylene conversion compared to styrene
(Figure 6).
CONCLUSION
Ru3(CO)9-dpam (diphenyl arsino methane) derivatives,
such as complexes (1)–(3) are successfully synthesized by
two step method. The single crystal X-ray diffraction study
confirms their crystal structures. The complex (3) trifluro
triphenyl derivative of Ru3(CO)9-dpam showed the effective
conversion for alkenes and moderate conversion for alkyne,
compared to other complexes(1) and (2). Higher hydrogena-
tion activity was observed by tuning the reaction condition
such as increasing the hydrogen pressure, adopting suitable
toluene solvent in the presence of as prepared Ru-organometallic
complexes.
FIG. 5. Catalytic hydrogenation of Cyclohexene on complex (3) in different
solvent and pressure conditions at fixed reaction time = 5h.
corresponding electron withdrawing and electron donating
groups, attached to the tri ruthenium carbonyl complex
(Table 2). Electron donating group (methyl) strengthens the
ruthenium cluster, and it favors the cluster catalysis, whereas
electron withdrawing group weakens the cluster and favors the
fragmentation catalysis (methoxy).
Figure 5 shows the solvent effect for hydrogenation of cyclo-
hexene in the presence of complex (3) catalyst, at different pres-
sure condition with constant reaction temperature. The higher
hydrogen solubility nature of toluene solvent showed higher
conversion for cyclohexene conversion compared to hexane
solvent. Increase in hydrogen pressure, increases the catalytic
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