Polymorphism and thermodynamic properties of chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) complex

Article abstract of DOI:10.1016/j.jorganchem.2016.01.008

A new crystalline polymorph of known chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) complex [RuCl(PPh₃)₂(η⁵-C₅H₅)] was obtained and characterized by various analytical methods including

Full text of DOI:10.1016/j.jorganchem.2016.01.008

Accepted Manuscript
Polymorphism and thermodynamic properties of
chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) complex
Elena V. Gorbachuk, Elena K. Badeeva, Ruzal G. Zinnatullin, Pavel O. Pavlov, Alexey
B. Dobrynin, Aidar T. Gubaidullin, Marat A. Ziganshin, Alexander V. Gerasimov, Oleg
G. Sinyashin, Dmitry G. Yakhvarov
PII:
S0022-328X(16)30008-0
10.1016/j.jorganchem.2016.01.008
JOM 19359
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 30 September 2015
Revised Date: 10 December 2015
Accepted Date: 8 January 2016
Please cite this article as: E.V. Gorbachuk, E.K. Badeeva, R.G. Zinnatullin, P.O. Pavlov, A.B. Dobrynin,
A.T. Gubaidullin, M.A. Ziganshin, A.V. Gerasimov, O.G. Sinyashin, D.G. Yakhvarov, Polymorphism and
thermodynamic properties of chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) complex,
Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2016.01.008.
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ACCEPTED MANUSCRIPT
Graphical abstract: pictogram
Polymorphism and thermodynamic properties of
chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II)
complex
a,b,
a
a,b
a
Elena V. Gorbachuk
Elena K. Badeeva , Ruzal G. Zinnatullin
,
a,b
a
Pavel O. Pavlov , Alexey B. Dobrynin , Aidar T. Gubaidullin ,
b
b
a
Marat A. Ziganshin , Alexander V. Gerasimov , Oleg G. Sinyashin ,
a,b,*
Dmitry G. Yakhvarov
The graphical abstract pictogram.
1

ACCEPTED MANUSCRIPT
Polymorphism and thermodynamic properties of
chloro(cyclopentadienyl)bis(triphenylphosphine)-
ruthenium(II) complex
a,b
a
Elena V. Gorbachuk , Elena K. Badeeva , Ruzal G.
a,b
a,b
a
Zinnatullin , Pavel O. Pavlov , Alexey B. Dobrynin ,
a
b
Aidar T. Gubaidullin , Marat A. Ziganshin , Alexander V.
b
a
a,b,
Gerasimov , Oleg G. Sinyashin , Dmitry G. Yakhvarov
*
a
A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan
Scientific Centre of the Russian Academy of Sciences, Kazan,
420088, Russian Federation
b
Kazan Federal University, A.M.Butlerov Institute of Chemistry,
Kazan, 420008, Russian Federation
Keywords:
cyclopentadienide-anion,
polymorphism,
ruthenium
complexes, thermodynamic properties, triphenylphosphine
-
-------------
*
Corresponding author.
E-mail address: yakhvar@iopc.ru (D.G. Yakhvarov)
1

ACCEPTED MANUSCRIPT
A B S T R A C T
A
new
crystalline
polymorph
of
known
chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II)
5
complex [RuCl(PPh ) (η -C H )] was obtained and characterized by
3
2
5 5
various analytical methods including single-crystal and powder X-
ray diffraction (XRPD) and differential scanning calorimetry (DSC)
in combination with thermo-gravimetric analysis (TG-DSC). The
obtained crystals of new polymorph are monoclinic, space group
P2 /n, with a = 11.125(4), b = 19.184(6), c = 15.946(5) Å, α = 90,
1
β = 100.174(5), γ = 90, and Z = 4. It has been found that real
melting point of the complex (M.p. = 252-253°C) can be determined
only in inert atmosphere while an apparent melting is observed in
the range 142-150°C due oxygen promoted oxidative dissociation of
triphenylphosphine ligand.
1. Introduction
The ruthenium complexes based on cyclopentadienyl ligand are
widely used in organic chemistry and have different applications
as homo- and heterogeneous catalysts and useful materials [1-3].
The
chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II)
5
complex [RuCl(PPh ) (η -C H )] (1) firstly prepared by Gilbert and
3
2
5 5
Wilkinson [4] is one of the most investigated and useful for
synthetic chemistry ruthenium compound [5-10]. However its solid
state properties are an object of several contradictions [11-15].
According to the published literature data, the experimentally
observed melting temperature of 1 has been found to be different.
Thus, Bruce reported the melting point determined for this
compound as 131-135°C [11] that is also supported by some
textbooks [16]. Meanwhile, Wilczewski claimed that the melting at
this temperature is occurring only in open capillary when the
complex starts melting at 135-138°C and completely melted at 180-
200°C, while the use of a sealed capillary results in melting
2

ACCEPTED MANUSCRIPT
point 236-248°C [14]. Unfortunately, up to present the driving
forces
understood as yet. In order to clarify this long scientific
discussion, we decided to synthesize and investigate the
of
these
incompatibilities
have
not
been
properly
properties of this very well known organometallic specie in solid
state.
In the present work we have found that complex 1 can be
crystallized in different polymorphic states: previously reported
polymorph 1a [13] and synthesized by us new polymorph 1b reported
in this communication. The properties of each polymorph in solid
state have been studied by single-crystal and powder X-Ray
diffraction (XRPD) and differential scanning calorimetry (DSC)
involving thermogravimetric and mass-spectrometry (TG/DSC/MS)
analysis.
2. Results and Discussion
2.1. Syntheses
5
The known polymorph of the ruthenium complex [RuCl(PPh ) (η -
3
2
C H )] 1а was obtained by previously described procedure [11] by
5
5
heating of a mixture of aqueous ruthenium(III) chloride (RuCl3
H2O), triphenylphosphine, and freshly obtained cyclopentadiene by
thermal cracking of its dimer in ethanol solution. The polymorph
b was obtained by fractional addition of the mentioned above
x
3
1
aqueous ruthenium salt to a boiling ethanol solution containing
cyclopentadiene and triphenylphosphine (Scheme 1). The crystals of
both polymorphs 1a and 1b suitable for X-ray crystal structure
analysis were obtained directly in the reaction medium without
special recrystallization procedure.
3

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Ru
RuCl x 3H O + 2 PPh + CpH
Ph P
3
3
2
3
Cl
Ph P
3
1
Scheme 1. Synthesis of complex 1.
2.2. Description of crystal structure
Both obtained polymorphs 1a and 1b were characterized by
various methods, including X-ray crystallography (Fig.1). The X-
ray crystal structure parameters obtained for 1a were found
identical to the previously described [13,15].
Fig.1. Overlay of the molecular structures of the complex units in
1a (red) and 1b (green). Hydrogen atoms have been omitted for
clarity.
The comparison of the X-ray data parameters obtained for
polymorphs 1a and 1b (Table 1) allowed us to find some differences
in the structure of the complex 1 in solid state. According to the
single-crystal X-ray structure analysis, main difference observed
for the molecules 1a and 1b is the orientation of the phenyl
groups of triphenylphosphine ligands (Fig.1). Thus, the longest
distances between the carbon atoms of phenyl groups A and B in 1a
is 4.19 Å in comparison with the value 3.825(3)Å in 1b. The angle
4

ACCEPTED MANUSCRIPT
of rotation of the benzene rings in 1a is 28.76°, while it is
significantly less in 1b (8.55°). It means that the phenyl rings A
and B of two triphenylphosphine ligands are almost parallel in 1b.
Moreover, in 1b the formed complex structure angels P(1)RuP(2)
100.05°, P(1)RuCl 91.32° and P(2)RuCl 91.48° are different from the
corresponding values reported for 1a by Bruce et al (103.99°,
9
0.41° and 89.05°, respectively) [13] and Wilczewski et al
103.88°, 90.52° and 88.90° respectively) [15] due to presence of
(
intramolecular π-π-interaction between the benzene rings of two
PPh ligands in the molecule of new polymorph 1b.
3
The analysis of the intermolecular interactions in both
crystals of 1a and 1b shows the presence of complex 3D-structure
-
that arises from C-H…π-interactions and additionally from C-H…Cl
in 1a (Fig.2).
Fig.2. Packing of the previously reported 1a and new 1b polymorphs.
5

ACCEPTED MANUSCRIPT
Table 1. Parameters of the crystal cell and selected bond lengths
(Å) and angles (°) for 1a and 1b.
1a
1b
Crystal cell parameters
Space group
P-1
P2 /n
1
a
b
c
α
β
γ
14.493(8)
11.315(4)
11.745(4)
69.99(3)
84.67
11.125(4)
19.184(6)
15.946(5)
90
100.174(5)
90
67.27(3)
2
Z
4
Bond lengths
Ru(1)-P(1)
Ru(1)-P(2)
P(1)-C(12)
P(2)-C(36)
Ru(1)-Cl(1)
2.3366
2.3353
1.8393
1.8536
2.4534
2.3202(14)
2.3143(15)
1.842(4)
1.826(4)
2.4622(14)
Bond angels
P(1)-Ru(1)-P(2)
Ru(1)-P(1)-C(12)
Ru(1)-P(2)-C(36)
Cl(1)-Ru(1)-P(1)
Cl(1)-Ru(1)-P(2)
103.99
125.70
118.58
89.05
100.05(4)
126.55(15)
119.89(15)
91.32(4)
90.41
91.48(4)
2.3. X-ray powder diffraction (XRPD)
A thermal stability of both polymorphs was studied by XRPD at
variable temperature up to 170°C. According to the obtained data
for 1b (Fig.3), the heating of the sample up to 150°C and
subsequent cooling don't cause a substantial change in the total
diffraction
pattern
which
is
clearly
identified
by
the
interference peaks corresponding to both polymorphs, though
6

ACCEPTED MANUSCRIPT
acquiring somewhat diffuse view as a result of the change in the
crystallite size and the deformation of some long-range order
therein. Further increasing of the temperature up to 170°C leads
to amorphization of the sample and disappearance of all reflexes
in the diffraction pattern of the crystal. This allows concluding
that increasing of the temperature higher than 150°C leads to the
destruction of this compound.
Fig.3. Experimental X-ray powder patterns for 1b at room
temperature (black curve) and after heating up to 100°C (orange
curve), 130°C (green curve), 150°C (brown curve) and 170°C (pale
green curve). At the bottom – theoretical XRD curve for polymorph
1b (blue curve) and polymorph 1a (red curve) calculated on the
basis of the X-Ray data [13].
It is interesting to note that for the sample representing
polymorph 1a, the diffraction pattern remains unchanged up to
temperature 150°C (Fig.4), but at this temperature additional
interference peaks at the angles of 11.5, 12.3 and 19.4° 2θ have
been observed. One would assume that at this temperature occurs
partial transition to a polymorph 1b, but in this case reflections
in the scattering angles 7.3 and 9.4° 2θ on the diffraction
pattern would be clearly observed.
7

ACCEPTED MANUSCRIPT
Fig.4. Experimental X-ray powder patterns for the sample 1a at
room temperature (red curve) and after heating up to 130° (blue
curve) and 150° C (green curve). At the bottom - theoretical XRD
curve for polymorph 1a (black curve) and polymorph 1b (brown
curve) calculated on the basis of the X-Ray data [13].
The performed experiments allow concluding that oxygen has a
crucial influence on the temperature of the observed phase
transition. Thus, the solid-liquid transition observed in the
presence of air in the range 140-145°C for both polymorphs is not
real melting process. Indeed, the careful study of the solid-
liquid transition at this temperature allows to determine the
formation of colourless crystals formed by sublimation. Applying
of the single crystal X-ray diffraction towards the analysis of
the nature of the formed new crystals allows to conclude that
these
crystals
are
one
of
the
crystalline
form
of
triphenylphosphine oxide Ph PO (a = 29.120(2), b = 9.143(1), c =
3
11.252(1), Space group Pbca) [17], formed by oxygen promoted
oxidative decoordination of triphenylphosphine ligand from the
coordination sphere of ruthenium in complex 1 during experiment.
Note, the literature melting point data obtained for Ph PO 155-
3
158.8°C [18] is slightly higher than the temperature range of the
8

ACCEPTED MANUSCRIPT
destruction of the complex. Thus, the published by Bruce et al
melting point for complex 1 131-135°C [9, 10] is an apparent one
and arises from the melting of triphenylphosphine oxide formed by
oxidative decoordination of triphenylphosphine ligand from the
ruthenium center initiated by heating in the presence of oxygen.
And the real melting point can be determined only in inert (oxygen
free) atmosphere (argon, dry nitrogen etc.).
2.4. Differential scanning calorimetry
Additional proof of the melting temperature range was obtained
from DSC analysis. Thus, it was found that 1b sample melts at
52°C. The experimentally found enthalpy of melting is ꢀH = 46.5
2
-1
kJ mol . Moreover, the cooling of the molten complex results in
formation of glass due glass transition at 93°C (cooling rate 10°
-1
min ). Second heating gives glass transition at T = 95°C, the
g
cold crystallization of amorphous component with an onset at 161°C
-1
and M.p. = 241°C (ꢀH = 41.9 kJ mol ). The second cooling gives
crystallization in the range of 208-168°C (Fig.5).
Fig.5. DSC curves of two consecutive heating and cooling runs for
polymorph 1b.
9

ACCEPTED MANUSCRIPT
First heating of 1a gives a slightly higher melting point
-
1
2
53°C and enthalpy of melting (ꢀH = 47.8 kJ mol ). First cooling
leads to partial crystallization in the range of from 180°C to
47°C (crystallization of about 50% molecules occurs) with less
1
-1
glass transition at 95°C at a cooling rate of 10° min . Second
heating gives glass transition at Tg 95°C, the cold
crystallization of amorphous component with an onset at 134°C
=
-1
followed by the melting beginning at 245°C (ꢀH = 42.1 kJ mol )
Fig.6).
(
Fig.6. DSC curves of two consecutive heating and cooling runs for
polymorph 1a.
It should be noted that no polymorphic transition and no
weight loss of the investigated samples have been observed in
TG/DSC/MS experiments even by heating up to 250°C (see electronic
supplementary material, Figs. S2 and S3).
2.5. Conclusions
Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II)
5
complex [RuCl(PPh ) (η -C H )] forms two polymorphs displaying
3
2
5 5
1
0

ACCEPTED MANUSCRIPT
different crystal packing and physico-chemical properties. The
observed polymorphism provides an opportunity to examine the
thermodynamic properties depending on the complex structure and
its thermal stability. The real melting point of the investigated
complex can be determined only in inert atmosphere due possibility
of oxygen promoted oxidative dissociation of triphenylphosphine
ligand. These results nicely complement previously described
5
thermal
properties
of
the
investigated
[RuCl(PPh ) (η -C H )]
3
2
5 5
complex [11-15].
3. Experimental
3.1. General Procedures
Main manipulations and chemical reactions were carried out
under an atmosphere of dry nitrogen. All solvents were purified
and dried prior to use. Ethanol, petroleum ether and diethyl ether
were dried with sodium followed by distillation under dry
nitrogen. Ruthenium trichloride trihydrate (RuCl ·x 3H O, Alfa
3
2
Aesar), triphenylphosphine (Sigma-Aldrich) and dicyclopentadiene
(Acros Organics) were commercial products.
NMR spectra were measured at ambient temperature on a Bruker
1
13
MSL-500 (500.13 МHz, Н; 125.7 MHz, C) and Bruker MSL-400 (161.97
31
MHz,
Р) spectrometers in deuterated chloroform. IR spectra were
recorded on a FTIR spectrometer Tensor 27 (Bruker) in the 4000-400
-1
-1
cm
middle IR range at an optical resolution of 4 cm . Solid
samples were prepared as KBr pellets. Far-IR spectra were recorded
-1
on a FTIR spectrometer IFS-66v/s (Bruker) in the 600-100 cm range
-
1
at an optical resolution of 4 cm . Solid sample, mixed with nujol,
was placed between polyethylene plates. ESI-MS measurements were
performed using an AmazonX (Bruker Daltonics, Germany) ion trap
mass spectrometer in positive mode in the mass range of 250–2000
Da. The optimized ESI-MS conditions were as follows: capillary
-1
voltage, –4.5 kV; nitrogen drying gas, 10 L min , 300°C. Melting
1
1

ACCEPTED MANUSCRIPT
points were measured with Stanford Research System MPA-100
OptiMelt.
X-ray powder diffraction (XRPD) measurements were performed on
a Bruker D8 Advance diffractometer equipped with Vario attachment
and Vantec linear PSD, using Cu radiation (40 kV, 40 mA)
monochromated by the curved Johansson monochromator (λCu Kα1 1.5406
Å). Room-temperature data were collected in the reflection mode
with a flat-plate sample. The samples were loaded on a standard
zero diffraction silicon plate, which was kept spinning (15 rpm)
throughout the data collection. Patterns were recorded in the 2θ
o
o
o
range between 3 and 90 , in 0.008 steps, with a step time of 0.3–
.0 s. Several diffraction patterns in various experimental modes
5
were collected and summed for the sample. Processing of the
obtained data performed using EVA software packages [19].
Differential scanning calorimetry (DCS) studies were performed
with DSC 204 F1 Phoenix (Netzsch). Sample of ruthenium complex was
placed in a standard aluminium crucible (40 ꢁL) with lid having a
hole with diameter of 0.5 mm. All experiments were made in argon
-1
-1
flow (150 mL min ) with heating and cooling rates of 10°C min
20]. Simultaneous method of thermogravimetry and differential
[
scanning calorimetry (TG/DSC/MS) was used in combination with mass
spectrometry of the evolved vapours. For this, a STA 449 C Jupiter
thermoanalyzer (Netzsch) with a QMS 403 C Aёolos quadrupolarmass-
spectrometer (Netzsch) were used. Experiments were conducted at a
-1
-1
heating rate of 10°C min in an argon flow of 75 mL min .
3.2. Synthesis of 1a and 1b
Polymorph 1a was prepared according to the previously
described method [11] using 1.31 g (5.0 mmol) of RuCl x 3H O, 4.00
3
2
g (15.2 mmol) of triphenylphosphine and 2.6 mL (30.9 mmol) of
freshly distilled cyclopentadiene. This slightly modified
procedure has been also used for the synthesis of polymorph 1b.
For preparation of 1b a solution containing 1.31 g (5.0 mmol) of
RuCl3 x 3H O in 17.4 mL of ethanol was added in two steps (with
2
1
2

ACCEPTED MANUSCRIPT
interval
containing 4.00 g (15.2 mmol) of triphenylphosphine and 2.6 mL
30.9 mmol) of cyclopentadiene. After that the resulting mixture
6
hours) to
a
boiling ethanol solution (180 mL)
(
was additionally refluxing for 10 hour and slowly cooled to room
temperature. After one night the orange crystals suitable for
single-crystal X-ray analysis were collected and successively
washed with ethanol (2 х 10 mL), petroleum ether (2 х 10 mL) and
diethyl ether (2 х 10 mL). The obtained solid was dried in vacuum
o
prior to NMR and IR studies (1.71 g, 47%). M.p. 245-252 C
1
(
capillary, argon). NMR (δ, chloroform-d): H (500.13 МHz) 7.38 m,
13
1
7
.25 m, 7.15 m (30H, P(C H ) ), 4.11 (s, 5H, C H );
C{ H} (125.7
6
5 3
5 5
1
2
MHz) 138 (t, J = 19.1 Hz, ipso-C H ), 133.8 (t, J = 5.0 Hz, o-
CP
6 5
CP
3
C H ), 128.6 (s, p-C H ), 127.5 (t, J
= 4.7 Hz, m-C H ), 81.4 (t,
6
5
6 5
CP
6 5
2
31
1
-1
JCP = 2.3 Hz, C H );
P{ H} (161.9 MHz) 39.9 (s). IR (cm , KBr):
5 5
1586 (w), 1571 (w), 1480 (m), 1433 (s), 1182 (w), 1158 (w), 1089
-
(m), 998 (w), 834 (m), 804 (w), 749 (m), 695 (s), 519 (s). IR (cm
1
5
+
,
nujol): 277 (m) (Ru-Сl); ESI-MS, m/z: [Ru(PPh ) (η -C H )] 691.2.
3 2 5 5
-1
C H ClP Ru (M = 726.19 g mol ): calcd: C, 67.81; H, 4.86; Cl,
41 35
2
4
.88; P, 8.53; Ru, 13.92; found: C, 67.94; H, 5.09; Cl, 4.99; P,
.11; Ru, 13.87.
8
Acknowledgments
This work is financially supported by the Russian Science
Foundation (project 14-13-01122).
Appendix A. Supplementary material
For detailed procedure of the X-ray crystal structure
determination of 1b, see Online Supplementary Materials. CCDC
1
438379 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
1
3

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1
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Highlights
Polymorphism and thermodynamic properties of
chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II)
complex
a,b,
a
a,b
a
Elena V. Gorbachuk
Elena K. Badeeva , Ruzal G. Zinnatullin
,
a,b
a
Pavel O. Pavlov , Alexey B. Dobrynin , Aidar T. Gubaidullin ,
b
b
a
Marat A. Ziganshin , Alexander V. Gerasimov , Oleg G. Sinyashin ,
a,b,*
Dmitry G. Yakhvarov
Highlights.
►
New
polymorph
of
known
chloro(cyclopentadienyl)-
5
bis(triphenylphosphine)ruthenium(II) complex [RuCl(PPh ) (η -C H )]
3
2
5 5
has been synthesised and fully characterized. ► The real melting
5
point of [RuCl(PPh ) (η -C H )] complex has been determined. ► An
3
2
5 5
oxygen promoted oxidative dissociation of triphenylphosphine
ligand was observed.
1