Ionic liquid based Ru(II)-phosphinite compounds and their catalytic use in transfer hydrogenation: X-ray structure of an ionic compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol

Article abstract of DOI:10.1016/j.poly.2014.05.079

The compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride (1) was prepared from the reaction of 1-methylimidazole with epichlorohydrine. The corresponding phosphinite ligands were synthesized by the reaction 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride, [C₇H ₁₅N₂OCl]Cl with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, in anhydrous CH₂Cl₂ and under an inert argon atmosphere. [Ru(η⁶-arene)(μ-Cl)Cl] ₂ dimers readily react with the phosphinite ligands [(Ph ₂PO)-C₇H₁₄N₂Cl]Cl (2) or [(Cy ₂PO)-C₇H₁₄N₂Cl]Cl (3) at room temperature to afford the cationic derivatives [Ru((Ph₂PO)-C ₇H₁₄N₂Cl)(η⁶-arene)Cl ₂]Cl and [Ru((Cy₂PO)-C₇H₁₄N ₂Cl)(η⁶-arene)Cl₂]Cl {arene: benzene (4), (5); p-cymene (6), (7)}. The structures of these ligands and their corresponding complexes have been elucidated by a combination of multinuclear NMR and IR spectroscopy, TGA/DTA and elemental analysis. The molecular structure of the ionic compound 1 was also determined by an X-ray single crystal diffraction study. Furthermore, the catalytic activity of complexes 4-7 for the transfer hydrogenation of various ketones was investigated and these complexes were found to be efficient catalysts in the transfer hydrogenation of various ketones, with excellent conversions up to 99%. Specifically, [Ru((Cy₂PO)- C₇H₁₄N₂Cl)(η⁶-benzene)Cl ₂]Cl (5) and [Ru((Cy₂PO)-C₇H₁₄N ₂Cl)(η⁶-p-cymene)Cl₂]Cl (7) act as excellent catalysts, giving the corresponding alcohols in 98-99% conversions in 5 min (TOF ≤ 1188 h^-1).

Full text of DOI:10.1016/j.poly.2014.05.079

Polyhedron 81 (2014) 245–255
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Ionic liquid based Ru(II)–phosphinite compounds and their catalytic
use in transfer hydrogenation: X-ray structure of an ionic compound
1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol
c
c
d
a
Murat Aydemir a,b, , Khadichakhan Rafikova , Nurzhamal Kystaubayeva , Salih Paßsa , Nermin Meriç ,
⇑
Yusuf Selim Ocak b,d, Alexey Zazybin c, Hamdi Temel b,e, Nevin Gürbüz f, Ismail Özdemir f
a Department of Science, Faculty of Science, University of Dicle, 21280 Diyarbakir, Turkey
b Science and Technology Application and Research Center (DUBTAM), Dicle University, Diyarbakir 21280, Turkey
c Department of Chemical Engineering, Kazakh-British Technical University, 050000 Almaty, Kazakhstan
d Department of Chemistry, Faculty of Education, University of Dicle, 21280 Diyarbakir, Turkey
e Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Dicle University, Diyarbakir 21280, Turkey
f
_
Department of Chemistry, Faculty of Science and Art, University of Inönü, 44280 Malatya, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride (1) was prepared from the
reaction of 1-methylimidazole with epichlorohydrine. The corresponding phosphinite ligands were syn-
thesized by the reaction 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride, [C7H15N2OCl]Cl
with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, in anhydrous CH2Cl2
Received 29 April 2014
Accepted 27 May 2014
Available online 12 June 2014
and under an inert argon atmosphere. [Ru(
ligands [(Ph2PO)–C7H14N2Cl]Cl (2) or [(Cy2PO)–C7H14N2Cl]Cl (3) at room temperature to afford the cat-
ionic derivatives [Ru((Ph2PO)–C7H14N2Cl)(
6-arene)Cl2]Cl and [Ru((Cy2PO)–C7H14N2Cl)( 6-arene)Cl2]Cl
g l-Cl)Cl]2 dimers readily react with the phosphinite
6-arene)(
Keywords:
Ionic compound
Phosphinite
g
g
{arene: benzene (4), (5); p-cymene (6), (7)}. The structures of these ligands and their corresponding com-
plexes have been elucidated by a combination of multinuclear NMR and IR spectroscopy, TGA/DTA and
elemental analysis. The molecular structure of the ionic compound 1 was also determined by an X-ray
single crystal diffraction study. Furthermore, the catalytic activity of complexes 4–7 for the transfer
hydrogenation of various ketones was investigated and these complexes were found to be efficient cat-
alysts in the transfer hydrogenation of various ketones, with excellent conversions up to 99%. Specifically,
Transfer hydrogenation
X-ray
Ruthenium
[Ru((Cy2PO)–C7H14N2Cl)(g g
6-benzene)Cl2]Cl (5) and [Ru((Cy2PO)–C7H14N2Cl)( 6-p-cymene)Cl2]Cl (7) act
as excellent catalysts, giving the corresponding alcohols in 98–99% conversions in 5 min
(TOF 6 1188 hꢀ1).
Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction
and physical properties by selection of appropriate anion-cation
combinations [9]. Metal-containing ionic liquids are regarded as
Ionic liquids (ILs) are potential replacements for organic sol-
vents both on laboratory and industrial scales due to their green
characteristics, such as thermal stability, lack of vapor pressure,
non-flammability, wide liquid range, wide range of solubility and
miscibility [1–7]. They can be readily recycled, have a profound
effect on the activity and selectivity of reactions and in some cases,
facilitate the isolation of products. Therefore, ionic liquids are
considered viable substitutes for volatile organic solvents [8]. An
unusual feature of ionic liquids is the tunability of their chemical
promising new materials that combine the properties of ionic liq-
uids with additional intrinsic magnetic, spectroscopic or catalytic
properties, depending on the incorporated metal ion [10]. ILs that
contain palladium, ruthenium, platinum, gold and aluminum
(and also iron, nickel, zinc and copper) have been used with
success in catalysis [11,12]. Some metal (Pd, Ru, Rh, V) complex
catalysts with imidazolium tags [13–16] are also termed as IL
supported catalysts.
The chemistry of P-based ligands has also been intensively
explored in recent years [17,18]. Many improved phosphine
ligands and a variety of aminophosphine–phosphinite ligands have
important applications in organometallic chemistry and catalysis,
giving selective catalysts for hydroformylation, hydrosilylation
⇑
Corresponding author. Address: Department of Chemistry, Dicle University,
TR-21280 Diyarbakır, Turkey. Tel.: +90 412 248 8550x3028; fax: +90 412 248 8300.
E-mail address: aydemir@dicle.edu.tr (M. Aydemir).
http://dx.doi.org/10.1016/j.poly.2014.05.079
0277-5387/Ó 2014 Elsevier Ltd. All rights reserved.

246
M. Aydemir et al. / Polyhedron 81 (2014) 245–255
and transfer hydrogenation [19–21]. While much energy has been
devoted to the synthesis of aminophosphines and their metal
complexes, similar studies on the analogous phosphinites are less
extensive [22], even though some of their complexes have proved
to be efficient catalysts [23,24]. Though phosphine ligands have
found well-known applications in transition metal catalyzed
transformations [25,26], phosphinites afford different chemical,
electronic and structural properties compared to phosphines. The
metal–phosphorus bond is often stronger for phosphinites
compared to the related phosphine due to the presence of the elec-
tron-withdrawing P-OR group. In addition, the empty r⁄-orbital of
the phosphinite P(OR)R2 is stabilized, making the phosphinite a
better acceptor [27].
Catalytic transfer hydrogenation with the aid of a stable hydro-
gen donor is a useful alternative method for catalytic hydrogena-
tion by molecular hydrogen for the reduction of ketones [28,29].
In transfer hydrogenation, organic molecules, such as secondary
alcohols [30] or formic acid and its salts [31], have been employed
as the hydrogen source. The use of a hydrogen donor has some
advantages over the use of molecular hydrogen since it avoids
the risks and constraints associated with hydrogen gas as well as
the necessity for pressure vessels and other equipments. A variety
of transition metal complexes are known to catalyse hydrogen
transfer from an alcohol to a ketone [32]. Especially, over the last
three decades, most effort on hydrogenation has been focused on
the use of ruthenium catalysts. Transfer hydrogenation is usually
mediated by a complex bearing rhodium, ruthenium or iridium,
among which our focus has been ruthenium, because the ruthe-
nium catalysts have excellent performances [33,34]. Furthermore,
ruthenium has a cost advantage relative to other hydrogenation
metals such as rhodium and iridium [35,36].
Although a lot of phosphinite ligands and their derivatives have
been employed successfully as ligands in Ru(II)-promoted transfer
hydrogenation of ketones [37–39] and references therein], a
screening of the catalytic activities of ionic liquid based phosphi-
nites in this reaction has not been reported as yet. To the best of
our knowledge, there is no report on the utility of these complexes
including phosphinite ligands based on ionic liquids in Ru(II) cata-
lyzed transfer hydrogenation reactions. As a part of our interest in
the modular design of new ligand systems with different spacers to
control the electronic attributes at the phosphorus centers and to
investigate their coordination chemistry, in this paper, we report
Scheme 1. Synthesis of the compounds [C7H15N2OCl]Cl (1), [(Ph2PO)–C7H14N2Cl]Cl
(2), [(Cy2PO)–C7H14N2Cl]Cl (3), [Ru((Ph2PO)–C7H14N2Cl)(
6-benzene)Cl2]Cl (4),
[Ru((Cy2PO)–C7H14N2Cl)(
6-benzene)Cl2]Cl (5), [Ru((Ph2PO)–C7H14N2Cl)( 6-p-
cymene)Cl2]Cl (6) and [Ru((Cy2PO)–C7H14N2Cl)(
6-p-cymene)Cl2]Cl (7). (i) HCl,
epichlorohydrin, EtOH; (ii) 1 equiv. Ph2PCl or Cy2PCl, 1 equiv. n-BuLi, CH2Cl2; (iii) ½
equiv. [Ru( -Cl)Cl]2 or ½ equiv. [Ru( -Cl)Cl]2, CH2Cl2.
6-p-cymene)( 6-benzene)(
g
g
g
g
g
l
g
l
toward lower frequency (for details see Section 3). The structure of 1
was further confirmed by microanalysis, the results of which were
found to be in good agreement with the theoretical values.
Furthermore, the structure of 1 was elucidated by X-ray crystal-
lography, as follows. The colorless crystal of [C7H15N2OCl]Cl crys-
tallized in the monoclinic space group of P2(1). The unit cell
dimensions are a = 4.90220 Å, b = 14.1086 Å, c = 7.29760 Å. Its
asymmetric unit contains two molecules and has two-fold
crystallographic symmetry that can be expressed as a 2-fold screw
axis with direction [0,1,0] at 0,y,0 with screw component
[0,1/2,0]. Fig. 1 shows the asymmetric unit, which contains
(i) the ready synthesis of
a novel ionic liquid compound,
1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride, and
its corresponding phosphinite ligands, (ii) the synthesis and full
characterization of four half-sandwiches Ru(II)-arene complexes,
and (iii) for the first time their subsequent application in transfer
hydrogenation of various ketones.
2. Results and discussion
2.1. Synthesis of the compounds
The reaction of 1-methylimidazole and epichlorohydrin in etha-
nol at room temperature yields the compound 1-chloro-3-(3-
methylimidazolidin-1-yl)propan-2-ol chloride, [C7H15N2OCl]Cl (1)
(Scheme 1), which was characterized by elemental analysis, IR,
TGA-DTA and multinuclear NMR spectroscopies. The 1H and 13C
NMR spectral data of 1 are consistent with the proposed structure.
The 1H NMR spectrum of 1-chloro-3-(3-methylimidazolidin-1-
yl)propan-2-ol chloride exhibits
a characteristic signal at d
9.26 ppm for the –(CH3)NCHN–, group and two resonances at d
7.76. and 7.78 ppm for the –NCHCHN– protons, which are highly
deshielded. The IR spectrum also shows a broad absorption band
at 3357 cmꢀ1 for the O–H stretching, which is broadened and shifted
Fig. 1. The unit cell structure of 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-
ol chloride [C7H15N2OCl]Cl (1).

M. Aydemir et al. / Polyhedron 81 (2014) 245–255
247
Table 1
the 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride
Crystallographic data and structure refinement for [C7H15N2OCl]Cl (1).
ligand (1). The distance between the stereocenters of C(2)–C0(2)
in the packing structure is about 7.084 Å and some of selected
bond lengths are C(2)–C(3) 1.509 Å, C(3)–N(1) 1.462 Å, C(1)–Cl(1)
1.793 Å, N(2)–C(7) 1.459 Å and C(2)–O(1) 1.414 Å. The ionic chlo-
ride, which proves the ionic liquid structure of the compound, is
approximately 3.688 Å to the stereogenic C(2) atom. The structure
also has an intramolecular O(1)–H(1)ꢁ ꢁ ꢁCl(2) hydrogen bond with
bond distances of 0.82 and 3.075 Å and a bond angle of 166.93°.
The short contacts of the atoms, the intramolecular hydrogen
bonding interactions and the distances are calculated via MERCURY
3.0 and are shown in Fig. 2. Comprehensive crystal data for the
structure of 1 are given in Table 1 and the selected bond angles
are summarized in Table 2.
As a part of our ongoing research program for developing highly
active catalysts, we synthesized two novel ionic liquid based
phosphinite monodendate ligands. These phosphinite ligands,
[(Ph2PO)–C7H14N2Cl]Cl (2) and [(Cy2PO)–C7H14N2Cl]Cl (3) were
synthesized from the starting materials PPh2Cl and PCy2Cl, respec-
tively, in CH2Cl2 solution by the hydrolysis method [40,41]. The
LiCl salt was separated by filtration and the ligands were obtained
by extracting the solvent in vacuo in good yields. The progress of
this reaction was conveniently followed by 31P–{1H} NMR
spectroscopy. The signals of the starting materials, PPh2Cl at d
81.0 ppm and PCy2Cl at d 127.32 ppm, disappeared and new
singlets appeared downfield due to the phosphinite ligands. The
31P–{1H} NMR spectra of the phosphinites, [(Ph2PO)–C7H14N2Cl]Cl
(2) and [(Cy2PO)–C7H14N2Cl]Cl (3) show single resonances at d
118.46 and 148.76, respectively, (Fig. 3) [42–46] in line with the
values previously observed for similar compounds [47–50]. A solu-
tion of [(Ph2PO)–C7H14N2Cl]Cl (2) in CDCl3, prepared under aerobic
conditions, is stable for up to 18 h and then decomposes very
gradually to give the oxide and hydrolysis product diph-
enylphosphinous acid, Ph2P(O)H [51]. Furthermore, the 31P–{1H}
NMR spectrum also displays the formation of PPh2PPh2 and
P(O)Ph2PPh2, as indicated by signals at about d ꢀ15.2 ppm as a
Parameter
Empirical formula
M
C7H15Cl2N2O
213.10
Crystal system
Space group
a (Å)
b (Å)
c (Å)
monoclinic
P2(1)
4.90220(5)
14.1086(5)
7.29760(5)
90.00
a
(°)
b (°)
95.5720(5)
90.00
502.340(14)
2
1.409
0.604
0.50 ꢂ 0.25 ꢂ 0.16
2.80–33.46
ꢀ7 6 h 6 7,
ꢀ15 6 k 6 21,
ꢀ11 6 l 6 11
4919
c
(°)
V (Å3)
Z
Dcalc (g cmꢀ3
)
Absorption coefficient (Mo K
Crystal size (mm)
Theta range for data collection (°)
a
) (mmꢀ1
)
Index ranges
Reflections collected
Unique reflections (Rint
Completeness of theta = 25.50°
Refinement method
)
3078 (0.0144)
99.5%
full-matrix least-squares on F2
1831/26/109
Data/restraints/parameters
Goodness of fit (GOF) on F2
1.1040
Final R indices [I > 2
r
(I)]
R1 = 0.0397,
wR2 = 0.1556 I > 2
R1 = 0.0407,
r(I)
R indices
wR2 = 0.1559
0.554 and ꢀ0.250
Largest difference in peak and hole (e Åꢀ3
)
Additional material available from Cambridge Crystallographic Data Center as
deposition No: CCDC 986387 comprises H-atom coordinates, thermal parameters
and remaining bond lengths and angles.
1
singlet and d 35.6 ppm and d ꢀ21.4 ppm as doublets with J(PP)
226 Hz after 48 h [52]. On the contrary, a solution of [(Cy2PO)–C7
H14N2Cl]Cl (3) is unstable under aerobic conditions and undergoes
Fig. 2. The packing structure and short contacts of 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride [C7H15N2OCl]Cl (1).

248
M. Aydemir et al. / Polyhedron 81 (2014) 245–255
Table 2
[Ru(
ability of the {[Ru(arene)(
complexes of the general formula [Ru(
well-known [53]. As expected, the reaction of 2 and 3 with
[Ru( -Cl)Cl]2 or [Ru( -Cl)Cl]2 gave
6-benzene)( 6-p-cymene)(
corresponding complexes [Ru((Ph2PO)–C7H14N2Cl)(
6-arene)Cl2]Cl
and [Ru((Cy2PO)–C7H14N2Cl)(
6-arene)Cl2]Cl {arene: benzene (4),
g
6-p-cymene)(
l
-Cl)Cl]2 are also depicted in Scheme 1. The
-Cl)Cl]2} dimers to form mononuclear
6-arene)Cl2L] is
Selected bond angles (°) of compound [C7H15N2OCl]Cl (1).
l
g
Atoms
Angle
s.u.
Atoms
Angle
s.u.
H1–O1–C2
C3–N1–C4
C3–N1–C6
C4–N1–C6
C4–N2–C5
C4–N2–C7
C5–N2–C7
O1–C2–H2
O1–C2–C3
O1–C2–C1
H2–C2–C3
H2–C2–C1
C3–C2–C1
N1–C3–C2
N1–C3–H3A
N1–C3–H3B
C2–C3–H3A
C2–C3–H3B
H3A–C3–H3B
N1–C4–N2
N1–C4–H4A
N1–C4–H4B
N2–C4–H4A
N2–C4–H4B
H4A–C4–H4B
109.46
124.49
126.41
109.08
109.07
125.72
125.21
108.02
108.12
112.92
108.02
108.02
111.57
111.23
109.39
109.39
109.39
109.39
108.01
108.22
110.06
110.06
110.05
110.06
108.40
0.14
0.12
0.12
0.13
0.13
0.15
0.17
0.13
0.12
0.13
0.14
0.13
0.13
0.13
0.13
0.13
0.14
0.14
0.16
0.13
0.14
0.13
0.14
0.14
0.14
N2–C5–H5A
N2–C5–H5B
N2–C5–C6
H5A–C5–H5B
H5A–C5–C6
H5B–C5–C6
Cl1–C1–C2
Cl1–C1–H1A
Cl1–C1–H1B
C2–C1–H1A
C2–C1–H1B
H1A–C1–H1B
N1–C6–C5
N1–C6–H6A
N1–C6–H6B
C5–C6–H6A
C5–C6–H6B
H6A–C6–H6B
N2–C7–H7A
N2–C7–H7B
N2–C7–H7C
H7A–C7–H7B
H7A–C7–H7C
H7B–C7–H7C
110.36
110.36
106.80
108.59
110.36
110.36
112.25
109.15
109.16
109.15
109.15
107.87
106.82
110.36
110.36
110.36
110.36
108.59
109.47
109.47
109.47
109.48
109.48
109.47
0.16
0.17
0.17
0.19
0.18
0.16
0.11
0.14
0.13
0.16
0.15
0.17
0.14
0.16
0.15
0.20
0.16
0.18
0.20
0.21
0.23
0.24
0.23
0.25
g
l
g
l
g
g
(5); p-cymene (6), (7)}, respectively, in high yields as air stable,
red microcrystalline powders (Scheme 1). The phosphinite ligands
were expected to cleave the [Ru(benzene)Cl2]2 and [Ru(p-
cymene)Cl2]2 dimers to give the corresponding complexes via
monohapto coordination. The initial color change, i.e. from clear
orange to deep red, is attributed to the dimer cleavage, most prob-
ably by the phosphinite ligand [54]. The chemical purity of the
complexes was confirmed by single 31P–{1H} NMR signals at d
127.82, 157.21, 124.23 and 154.25, respectively (CDCl3) (Fig. 4).
These complexes are highly soluble in CH2Cl2 and slightly soluble
in hexane, so they can be crystallized from a CH2Cl2/hexane solu-
tion. The 1H NMR spectra of complexes 4 and 5 display the (–(CH3)-
NCHN–) resonances as broad signals at d 8.95 and 9.02 ppm and
the C6H6 protons as singlets at d 5.55 and 5.96 ppm, respectively.
In the 13C NMR spectra of 4 and 5, the (–(CH3)NCHN–) carbon
signals were observed at d 137. 10 and 137.59 ppm and the C6H6
carbon resonances were seen at d 88.10 (s) and 88.11 (s) ppm,
respectively. Furthermore, in the 13C–{1H} NMR spectra of these
complexes, J(31P–13C) coupling constants of the carbons of the phe-
nyl rings were observed, which is consistent with the literature
values [55]. The structures of the complexes were further con-
firmed by IR spectroscopy and microanalysis, and were found to
be in good agreement with the theoretical values. Other pertinent
spectroscopic and analytic data are given in Section 3.
[i: ꢀx,y,½ ꢀ z].
fast decomposition. Because compound 3 is not stable enough in
solution, the corresponding ruthenium(II) complexes were synthe-
sized in-situ. The appropriate assignment of the 1H chemical shifts
was derived from 2D HH-COSY spectra and that of the 13C chemical
ones from DEPT and 2D HMQC spectra. The structures for these
ionic based monodendate phosphinite ligands are consistent with
the data obtained from 1H and 13C NMR, IR spectra and elemental
analyses (for details see Section 3).
The starting complex [Ru(
by the reaction of the commercially available
(5-isopropyl-2-methylcyclohexa-1,3-diene) with RuCl3 [56]. The
reactions of [Ru( -Cl)Cl]2 with ligands 2 and 3 are
6-p-cymene)(
depicted in Scheme 1. The reactions of [Ru( -Cl)Cl]2
6-p-cymene)(
with two equivalents of 2 and 3 in CH2Cl2 at room temperature gave
g
6-p-cymene)(
l-Cl)Cl]2 was prepared
a
-phellandrene
g
l
g
l
Reactions of the ionic based monodendate phosphinites
with the metal precursors [Ru(g l-Cl)Cl]2 and
6-benzene)(
Fig. 3. The 31P–{1H} NMR spectra of the ligands [(Ph2PO)–C7H14N2Cl]Cl (2) and [(Cy2PO)–C7H14N2Cl]Cl (3) (CDCl3).

M. Aydemir et al. / Polyhedron 81 (2014) 245–255
249
Fig. 4. The 31P–{1H} NMR spectra of the complexes [Ru((Ph2PO)–C7H14N2Cl)(
g
6-benzene)Cl2]Cl (4), [Ru((Cy2PO)–C7H14N2Cl)(
g
6-benzene)Cl2]Cl (5), [Ru((Ph2PO)–
C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl (6) and [Ru((Cy2PO)–C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl (7) (CDCl3).
the red compounds [Ru((Ph2PO)-C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl
2.2. Thermal investigation (DTA)
(6) and [Ru((Cy2PO)–C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl (7), respec-
tively, in high yields. The structures of the P-coordinated complexes
6 and 7 are supported by elemental analysis as well as spectro-
scopic data. The 1H NMR spectral data of the complexes are
consistent with the proposed structures and their 1H NMR spectra
are different from those of ligands 2 and 3. Furthermore, the 1H
The thermal behavior of the compounds [Ru((Ph2PO)-C7H14N2Cl)
6-benzene)Cl2]Cl (4), [Ru((Cy2PO)-C7H14N2Cl)( 6-benzene)Cl2]Cl
(5), [Ru((Ph2PO)-C7H14N2Cl)(
6-p-cymene)Cl2]Cl (6) and [Ru((Cy2
PO)–C7H14N2Cl)(
6-p-cymene)Cl2]Cl (7) was investigated in two
(g
g
g
g
steps under nitrogen and oxygen atmospheres with a heating rate
of 20 °C minꢀ1 over a temperature range 25–900 °C. The first step
was applied with N2 from 25 to 800 °C, and the second step pro-
ceeded under O2 between 800 and 900 °C. The thermal stability of
the compounds changes from one to another. It was seen that the
compounds remained quite tough until 174, 164, 190 and 173 °C
for 4–7, respectively. The weight losses were calculated and evalu-
ated with TA60 software in accordance with the peaks. Each of the
computations with an exact percentage of the total was indicated
on the thermograms, as depicted in the Supporting information
(Figs. 5–8). The peaks pointing downwards on the graphic are endo-
thermic and are due to the leaving substituted groups. The sudden
increase of peaks after 800 °C is the result of burning organic
fragments, such as imidazole, phenyl, cyclohexyl, p-cymene and
benzene, which can be removed step by step.
NMR spectra of the complexes display signals for the
g
6-p-cymene
group together with the resonances for the protons of the
P-coordinated ligands. The arene signals are well resolved and show
only H–H coupling, as found in previously reported mononuclear
g
6-p-cymene compounds [57,58]. The 1H and 13C NMR spectra of
the complexes display all the signals of the coordinated ligands.
In the 1H NMR spectra, aromatic CH protons of the p-cymene moi-
ety generally give two signals. It is very well-known that the pres-
ence of one (broad) or two signals due to aromatic CH of p-cymene
protons in the 1H NMR spectra of 6 and 7 is consistent with a Cs
symmetry of the complexes and free rotation of the arene
(p-cymene) ligand [59,60]. Furthermore, The 1H NMR spectra of 6
and 7 are characterized by isopropyl methyl doublets of the
p-cymene groups, at
d d
0.99 ppm (d, 6H, 3J = 6.8 Hz) and
0.87 ppm (d, 6H, J = 6.5 Hz), respectively. In their 13C–{1H} NMR
spectra, J(31P–13C) coupling constants of the carbons of the phenyl
rings are observed, which are consistent with the literature values
[61,62]. As expected, the coupling between i-carbons and the
phosphorus in 6 and 7 is relatively large, 1J(31P–13C) 52.3 and
29.7 Hz, for i-P(C6H5)2) and CH of P(C6H11)2), respectively. The most
relevant signals of the 13C–{1H} NMR spectra of the complexes are
those of the arene ligands (p-cymene) (for details see Section 3).
Although, single crystals of both complexes were obtained by slow
diffusion of diethyl ether into a solution of the compound in
dichloromethane over several days, unfortunately they lost
their regular and transparent structures for X-ray diffraction
analysis.
2.3. Catalytic transfer hydrogenation of various ketones
The good catalytic performance and the higher structural
permutability of phosphinite based transition metal complexes
[63–65,38,66] prompted us to develop new Ru(II) complexes with
well-shaped modified phosphinite ligands [67–70]. We paid partic-
ular attention to arene ligands [71], because (i) the spectator
ligands automatically occupy three adjacent coordination sites of
the ruthenium centre in an octahedral coordination environment,
leaving three facial sites for other functions, (ii) arene ligands that
are relatively weak electron donors may provide a unique reactiv-
ity on the metallic center, and (iii) the substitution pattern on the

250
M. Aydemir et al. / Polyhedron 81 (2014) 245–255
ring is flexible. Complexes 4–7 were tested as catalysts in transfer
hydrogenation of aromatic ketones in a 2-propanol solution.
First of all, complexes 4–7 were used as precatalysts, 2-propanol/
KOH as the reducing system, and acetophenone as the model sub-
strate. The results of the catalytic test reactions are listed in Table 3.
At room temperature, no significant formation of 1-phenylethanol
was observed (Table 3, Entries 2, 7, 12 and 17). Furthermore, as
can be inferred from Table 3, the precatalysts as well as the presence
of KOH are necessary to observe appreciable conversions. The base
facilitates the formation of ruthenium alkoxide by abstracting a pro-
ton from the alcohol and subsequently the alkoxide undergoes b-
elimination to give ruthenium hydride, which is an active species
in this reaction [72–75]. As seen in Table 3, increasing the sub-
strate-to-catalyst ratio does not cause a decrease in the conversion
of the product in most cases. For instance, transfer hydrogenation
of acetophenone could be achieved with 98% yield even when the
substrate concentration was reduced from 0.1 to 0.05 or 0.01 M
and the substrate-to-catalyst ratio reached 1000:1 at reflux temper-
ature of the solvent, though with an increase in the reaction time
(Table 3).When the reaction carried out with a substrate-to-catalyst
ratio of 100:1 at reflux temperature, a smooth reduction of aceto-
phenone into 1-phenylethanol occurred, with a conversion of up
to 98% after 10 min for the reaction conducted with 5 and 7, and
30 min for those with 4 and 6. As seen in Table 3, a typical reduction
reaction of acetophenone indicates that the reaction rate is indepen-
dent of the type of arene moiety (benzene or p-cymene) bound to the
metal center, despite its dependence on the alkyl substituents on the
phosphorus atom. The results of the optimization studies
demonstrate obviously that both complexes, [Ru(Cy2POC7H14N2Cl)
addition, the catalytic efficiency was seen to be independent of the
type of arene moiety.
Encouraged by the activities obtained in these preliminary
studies, we next extended our investigations to include hydrogena-
tion of substituted acetophenone derivatives. The results in Table 4
indicate that a range of acetophenone derivatives can be hydroge-
nated with good conversions. The catalytic reductions of the aceto-
phenone derivatives were all carried out with the conditions
optimized for acetophenone, and complexes 4–7 showed high
activity for most of the ketones. The introduction of electron with-
drawing substituents, attached to the aryl ring of the ketone,
reduced the electron density of the C@O bond so that the activity
was improved, giving rise to easier hydrogenation [76,77]. Com-
paring the catalytic performance to analogous complexes, the ionic
liquid based Ru(II)–phosphinite complexes can possibly form a
more stable catalytic transition state [78–81]. The catalytic activity
of the complexes is higher than that recently reported for related
half-sandwich complexes [82], and references therein].
Due to these efficient findings in the transfer hydrogenation of
acetophenone derivatives, we next extended our investigations to
include hydrogenation of various simple ketones. Examination of
the catalytic activity of these complexes has shown that they are
efficient catalysts, affording almost quantitative transformation
of the ketones in short times (Table 5). For instance, hydrogena-
tions of cyclohexanone and cyclopentanone could be achieved
approximately in 20 min by [Ru(Cy2POC7H14N2Cl)(
g
6-ben-
zene)Cl2]Cl (5) and [Ru(Cy2POC7H14N2Cl)(
g
6-p-cymene)Cl2]Cl (7).
Conversion of methyl isobutyl ketone occurred in 1 h by 5 and 7,
while that of diethyl ketone occurred in 2 h by 5 and 7. The cata-
(g
6-benzene)Cl2]Cl (5) and [Ru(Cy2POC7H14N2Cl)(
g
6-p-cymene)Cl2]
lytic activities of [Ru(Cy2POC7H14N2Cl)(
[Ru(Cy2POC7H14N2Cl)(
6-p-cymene)Cl2]Cl (7) were generally
g
6-benzene)Cl2]Cl (5) and
Cl (7), including a Cy moiety on the phosphorus atom, are active
g
and efficient catalysts leading to nearly quantitative conversions. In
higher in the studied hydrogen transfer reactions.
We conducted further experiments to investigate the influence
of the bulkiness of alkyl groups on the catalytic activity and the
results are given in Table 6 (Entries 1–16). A variety of simple aryl
alkyl ketones were transformed to the corresponding secondary
alcohols, and it was found that the activity is highly dependent
on the steric hindrance of the alkyl group. The reactivity
gradually decreased by increasing the bulkiness of the alkyl
groups [83–86].
Table 3
Transfer hydrogenation of acetophenone with 2-propanol catalyzed [Ru((Ph2PO)-
C7H14N2Cl)(g g
6-benzene)Cl2]Cl, (4), [Ru((Cy2PO)-C7H14N2Cl)( 6-benzene)Cl2]Cl, (5),
[Ru((Ph2PO)-C7H14N2Cl)(
cymene)Cl2]Cl, (7).
g
6-p-cymene)Cl2]Cl, (6) and [Ru((Cy2PO)-C7H14N2Cl)(
g
6-p-
g
Entry
Catalyst
S/C/KOH
Time
Conversion (%)f
TOF (hꢀ1
)
1
2
3
4
5
4a
4b
4c
4d
4e
100:1:5
100:1:5
100:1
500:1:5
1000:1:5
30 min
48 h
48 h
2 h
97
<5
<5
97
98
194
–
–
243
327
3. Experimental
3 h
3.1. Materials and methods
6
7
8
9
10
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
7a
7b
7c
7d
7e
100:1:5
100:1:5
100:1
500:1:5
1000:1:5
10 min
48 h
48 h
30 min
1 h
98
<5
<5
98
97
588
–
–
980
970
Unless otherwise stated, all reactions were carried out under an
atmosphere of argon using conventional Schlenk glass-ware, sol-
vents were dried using established procedures and distilled under
argon immediately prior to use. Analytical grade and deuterated
solvents were purchased from Merck. PPh2Cl, PCy2Cl, epichlorohy-
drin and 1-methylimidazole were purchased from Fluka and used
11
12
13
14
15
100:1:5
100:1:5
100:1
500:1:5
1000:1:5
30 min
48 h
48 h
2 h
95
<5
<5
97
98
190
–
–
243
327
as received. The starting materials [Ru(
g l-Cl)Cl]2
6-p-cymene)(
3 h
[87,88] and [Ru( -Cl)Cl]2 [89] were prepared accord-
g
6-benzene)(
l
16
17
18
19
20
100:1:5
100:1:5
100:1
500:1:5
1000:1:5
10 min
48 h
48 h
30 h
1 h
97
<5
<5
97
96
582
–
–
970
960
ing to literature procedures. FTIR spectra were recorded on an ATR
apparatus on a Perkin Elmer Spectrum 100 Fourier Transform
spectrophotometer and thermogravimetric analysis of the cata-
lysts was carried out on a Shimadzu DSC 60A thermal analyzer
up to 800–900 °C at a heating rate of 20 °C minꢀ1 under a nitrogen
atmosphere. 1H (400.1 MHz), 13C NMR (100.6 MHz) and 31P–{1H}
NMR (162.0 MHz) spectra were recorded on a Bruker AV400
spectrometer, with d referenced to external TMS and 85% H3PO4
respectively. Elemental analysis of carbon, hydrogen and nitrogen
Reaction conditions:
a
Refluxing in 2-propanol; acetophenone/Ru/KOH.
At room temperature; acetophenone/Ru/KOH.
Refluxing in 2-propanol; acetophenone/Ru, in the absence of base.
Refluxing in 2-propanol; acetophenone/Ru/KOH.
Refluxing in 2-propanol; acetophenone/Ru/KOH.
Determined by GC (three independent catalytic experiments).
b
c
d
e
f
was carried out on
a Costech Combustion System CHNS-O
g
Referred at the reaction time indicated in column; TOF= (mol product/mol
instrument. Melting points were recorded by a Gallenkamp Model
apparatus with open capillaries.
Ru(II)Cat.) ꢂ hꢀ1
.

M. Aydemir et al. / Polyhedron 81 (2014) 245–255
251
Table 4
Transfer hydrogenation results for substituted acetophenones with the catalyst systems, [Ru((Ph2PO)-C7H14N2Cl)(
g
6-benzene)Cl2]Cl, (4), [Ru((Cy2PO)-C7H14N2Cl)
(g
6-benzene)Cl2]Cl, (5), [Ru((Ph2PO)-C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl, (6) and [Ru((Cy2PO)-C7H14N2Cl)( 6-p-cymene)Cl2]Cl, (7).a
g
O
OH
OH
O
Cat 4-7
R
R
+
+
c
Entry
R
Time
Conversion (%)b
TOF(hꢀ1
)
Cat: Ru(II) complex, 4
1
2
3
4
5
4-F
4-Cl
4-Br
2-MeO
4-MeO
15 min
15 min
30 min
1 h
97
98
95
97
96
388
392
190
97
45 min
128
Cat: Ru(II) complex, 5
6
7
8
9
4-F
4-Cl
4-Br
2-MeO
4-MeO
5 min
5 min
10 min
20 min
15 min
99
97
98
95
96
1188
1164
588
285
384
10
Cat: Ru(II) complex, 6
11
12
13
14
15
4-F
4-Cl
4-Br
2-MeO
4-MeO
15 min
15 min
30 min
1 h
96
97
97
98
96
384
388
194
98
45 min
128
Cat: Ru(II) complex, 7
16
17
18
19
20
4-F
4-Cl
4-Br
2-MeO
4-MeO
5 min
5 min
10 min
20 min
15 min
98
97
97
96
96
1176
1164
582
288
384
a
Catalyst (0.005 mmol), substrate (0.5 mmol), 2-propanol (5 mL), KOH (0.025 mmol%), 82 °C, the concentration of acetophenone derivatives is 0.1 M.
b
c
Purity of compounds is checked by 1H NMR and GC (three independent catalytic experiments), yields are based on methyl aryl ketone.
TOF = (mol product/mol Cat.) ꢂ hꢀ1
.
Table 5
Transfer hydrogenation of various simple ketones with 2-propanol catalyzed by [Ru((Ph2PO)-C7H14N2Cl)(
[Ru((Ph2PO)-C7H14N2Cl)(
g
6-benzene)Cl2]Cl, (4), [Ru((Cy2PO)-C7H14N2Cl)(
g
6-benzene)Cl2]Cl, (5),
g
6-p-cymene)Cl2]Cl (6) and [Ru((Cy2PO)-C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl, (7).a
O
O
O
O
a
Entry
b
Cat.
c
d
c
Substrate
Time
Conversion (%)b
TOF (hꢀ1
)
1
2
3
4
5
6
7
8
4
4
4
4
5
5
5
5
6
6
6
6
7
7
7
7
a
b
c
d
a
b
c
d
a
b
c
d
a
b
c
60 min
60 min
3 h
96
97
98
98
97
99
98
96
99
98
96
97
96
98
96
99
96
97
33
16
291
297
98
48
99
98
32
16
288
297
96
6 h
20 min
20 min
1 h
2 h
9
60 min
60 min
3 h
10
11
12
13
14
15
16
6 h
20 min
20 min
1 h
d
2 h
50
a
Refluxing in 2-propanol; ketone/Ru/KOH, 100:1:5.
b
c
Determined by GC (three independent catalytic experiments).
Purity of compounds is checked by 1H NMR and GC (three independent catalytic experiments), yields are based on methyl aryl ketone.

252
M. Aydemir et al. / Polyhedron 81 (2014) 245–255
Table 6
Transfer hydrogenation results for substituted alkyl phenyl ketones with the catalyst systems [Ru((Ph2PO)-C7H14N2Cl)(
g
6-benzene)Cl2]Cl, (4), [Ru((Cy2PO)-C7H14N2Cl)
(g
6-benzene)Cl2]Cl, (5), [Ru((Ph2PO)-C7H14N2Cl)(
g
6-p-cymene)Cl2]Cl, (6) and [Ru((Cy2PO)-C7H14N2Cl)( 6-p-cymene)Cl2]Cl, (7).a
g
O
OH
OH
O
R
R
Cat 4-7
+
+
c
Entry
R
Time
Conversion (%)b
TOF(hꢀ1
)
Cat: Ru(II) complex, 4
1
2
3
4
ethyl
propyl
iso-propyl
ter-butyl
40 min
60 min
2 h
97
98
95
98
146
98
48
3 h
33
Cat: Ru(II) complex, 5
5
6
7
8
ethyl
propyl
iso-propyl
ter-butyl
15 min
20 min
40 min
1 h
95
97
98
96
380
291
147
96
Cat: Ru(II) complex, 6
9
10
11
12
ethyl
propyl
iso-propyl
ter-butyl
40 min
60 min
2 h
96
98
98
99
144
98
49
3 h
33
Cat: Ru(II) complex, 7
13
14
15
16
ethyl
propyl
iso-propyl
ter-butyl
15 min
20 min
40 min
1 h
98
97
96
95
392
291
144
95
a
Catalyst (0.005 mmol), substrate (0.5 mmol), 2-propanol (5 mL), KOH (0.025 mmol%), 82 °C, respectively, the concentration of alkyl phenyl ketones is 0.1 M.
b
c
Purity of compounds is checked by 1H NMR and GC (three independent catalytic experiments), yields are based on methyl aryl ketone.
TOF = (mol product/mol Cat.) ꢂ hꢀ1
.
3.2. Transfer hydrogenation of ketones
high vacuum, to yield a liquid that became more viscous upon
extensive drying, and this was was recrystallized from ethylacetate
at 0 °C. The precipitated product was filtered and dried in vacuo
yielding 1 as an off-white solid. Yield: 52.52 g, 98.1%; M.p.:
94–95 °C; 1H NMR (400.1 MHz, DMSO-d6, ppm) d: 9.26 (s, 1H,
(CH3)NCHN–), 7.78 and 7.76 (2xs, 2H, –NCHCHN–), 6.19 (d, 1H,
3J = 5.0 Hz, –CHOH), 4.42 (m, 1H, NCH2, (a)), 4.19 (m, 1H, NCH2,
(b)), 4.05 (br, 1H, –CHOH), 3.88 (s, 3H, CH3N), 3.65 (d, 2H,
3J = 3.6 Hz, –CH2Cl); 13C NMR (100.6 MHz, DMSO-d6, ppm) d:
36.20 (NCH3), 46.94 (–CH2Cl), 52.45 (NCH2), 69.07 (–CHOH),
123.47, 123.70 (–NCHCHN–), 137.62 ((CH3)NCHN–); assignment
was based on the 1H–13C HETCOR, DEPT and 1H–1H COSY spectra;
Typical procedure for the catalytic hydrogen transfer reaction: a
solution of the complexes [Ru((Ph2PO)-C7H14N2Cl)(
g
6-arene)Cl2]Cl
and [Ru((Ph2PO)-C7H14N2Cl)(
g
6-arene)Cl2]Cl {arene: benzene 4, 5;
p-cymene 6, 7} (0.005 mmol), KOH (0.025 mmol) and the corre-
sponding ketone (0.5 mmol) in degassed 2-propanol (5 mL) was
refluxed until the reactions were completed. Then, a sample of
the reaction mixture was taken off, diluted with acetone and ana-
lyzed immediately by GC. The conversions are related to the resid-
ual unreacted ketone. GC analyses were performed a Shimadzu
2010 Plus Gas Chromatograph equipped with a capillary column
(5% biphenyl, 95% dimethylsiloxane) (30 m ꢂ 0.32 mm ꢂ 0.25
l
m).
IR, (KBr, cmꢀ1
) m: 3357 (O-H), 3170, 3089 (aromatic C–H), 2985,
The GC parameters for transfer hydrogenation of the ketones were
as follows: initial temperature, 50 °C; initial time, hold min 1 min;
solvent delay, 4.48 min; temperature ramp 15 °C/min; final tem-
perature, 270 °C, hold min 5 min; final time, 20.67 min; injector
port temperature, 200 °C; detector temperature, 200 °C, injection
2856 (aliphatic C–H), 1575 (C@N), 1176 (C–N); Anal. for C7H15N2
OCl2 (214.11 g/mol): Calc. C, 39.27; H, 7.06; N, 13.08. Found: C,
39.18; H, 6.99; N, 13.00%.
3.3.2. Synthesis of [(Ph2PO)–C7H14N2Cl]Cl (2)
volume, 2.0 lL.
A dry and degassed CH2Cl2 (20 ml) solution of 1-chloro-3-(3-
methylimidazolidin-1-yl)propan-2-ol chloride (1) (0.100 g,
0.47 mmol) under an argon atmosphere was cooled to ꢀ78 °C in
an acetone and dry ice bath. To the cooled solution was added
dropwise a hexane solution of n-BuLi (0.293 ml, 0.47 mmol). After
the addition, the mixture was stirred at ꢀ78 °C for 1 h and then for
another 30 min at room temperature. The reaction solution was
cooled to ꢀ78 °C again and a solution of diphenylchlorophosphine
(0.105 g, 0.47 mmol) in CH2Cl2 (10 ml) was added dropwise to the
reaction medium. Stirring was continued for a further 1 h at
ꢀ78 °C, then the cooling bath was removed and the mixture was
stirred for another 1 h at room temperature. Precipitated lithium
chloride was removed by filtration under argon and then the vola-
tiles were evaporated in vacuo to leave a viscous oil of the phosph-
inite ligand 2. Yield 0.180 g, 96.8%; 1H NMR (400.1 MHz, CDCl3,
ppm) d: 10.14 (s, 1H, –(CH3)NCHN–), 7.13–7.78 (m, 12H,
3.3. Synthesis of the new compounds
3.3.1. Synthesis of 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol
chloride [C7H15N2OCl]Cl (1)
To
a
stirred solution of 1-methylimidazole (20.733 g,
250 mmol) in ethanol (40 mL) at room temperature was carefully
added concentrated hydrochloric acid (20.95 mL, 255 mmol). Cau-
tion: neutralization of a base with a strong acid is highly exothermic.
After addition of acid, the reaction mixture was cooled to room
temperature and epichlorohydrin (24.057 g, 260 mmol) was added
dropwise with stirring, while maintaining the temperature at
25 °C. The reaction vessel was then sealed and stirred at room tem-
perature for approximately 30 h. The solvent was removed under
reduced pressure on heating at 70 °C, followed by heating under

M. Aydemir et al. / Polyhedron 81 (2014) 245–255
253
P(C6H5)2 + –NCHCHN–), 4.94 (m, 1H, NCH2, (a)), 4.71 (br, 1H,
–CHOP), 4.57 (m, 1H, NCH2, (b)), 3.91 (m, 1H, –CH2Cl, (a)), 3.85
(m, 1H, –CH2Cl, (b)), 3.80 (s, 3H, NCH3); 13C NMR (100.6 MHz,
CDCl3, ppm) d: 36.55 (NCH3), 45.14 (–CH2Cl), 52.52 (NCH2), 78.45
(d, 2J = 23.1 Hz, (–CHOP), 122.59, 122.90 (–NCHCHN–), 129.53 (d,
3J31P–13C = 10.1 Hz, m-P(C6H5)2), 131.41 (p-P(C6H5)2), 135.26 (d,
2J31P–13C = 19.6 Hz, o-P(C6H5)2)), 138.17 ((CH3)NCHN–), 140.65 (d,
1J31P–13C = 47.8 Hz, i-P(C6H5)2); assignment was based on the
1H–13C HETCOR, DEPT and 1H–1H COSY spectra; 31P–{1H} NMR
(648.38 g/mol): C, 46.31; H, 4.66; N, 4.32. Found: C, 46.22; H,
4.57; N, 4.27%.
3.3.5. Synthesis of [Ru((Cy2PO)–C7H14N2Cl)(
[Ru( -Cl)Cl]2 (0.061 g, 0.12 mmol) and [(Cy2PO)
6-p-benzene)(
g
6-benzene)Cl2]Cl, (5)
g
l
–C7H14N2Cl]Cl (3) (0.100 g, 0.24 mmol) were dissolved in 25 mL of
dry CH2Cl2 under an argon atmosphere and stirred for 30 min at
room temperature. The volume of the solvent was then reduced
to 0.5 mL before addition of petroleum ether (10 mL). The precipi-
tated product was filtered and dried in vacuo yielding 5 as a dark
red solid. Yield 0.141 g, 87.6%; M.p.: 142–144 °C. 1H NMR
(400.1 MHz, DMSO-d6, ppm) d: 9.02 (s, 1H, –(CH3)NCHN–), 7.71,
7.54 (2xs, 2H, –NCHCHN–), 5.96 (s, 6H, aromatic protons of ben-
zene), 5.20 (br, 1H, –CHOP), 4.32 (br, 2H, NCH2), 3.82 (s, 3H,
NCH3), 3.54 (br, 2H, –CH2Cl), 2.42 (m, 2H, CH of P(C6H11)2), 1.29–
1.78 (m, 20H, CH2 of P(C6H11)2); 13C NMR (100.6 MHz, DMSO-d6,
ppm) d: 26.85, 26.94, 27.05, 28.08, 28.28, 28.56 (CH2 of
P(C6H11)2), 36.39 (NCH3), 45.75 (–CH2Cl), 46.93 (d, 1J = 28.5 Hz,
CH of P(C6H11)2), 49.98 (NCH2), 73.60 (d, 2J = 22.9 Hz, –CHOP),
88.11 (aromatic carbons of benzene), 123.06, 124.14 (–NCHCHN–),
137.59 (–(CH3)NCHN–); assignment was based on the 1H–13C HET-
COR, DEPT and 1H–1H COSY spectra; 31P–{1H} NMR (162.0 MHz,
DMSO-d6,ppm) d: 159.24; (CDCl3-d1, ppm) d: 157.21 (s, Ru–OPCy2);
(162.0 MHz, CDCl3, ppm) d: 118.46 (s, OPPh2); IR, (KBr, cmꢀ1
) m:
3053 (aromatic C–H), 1434 (P–Ph), 1060 (O–P); Anal. Calc. for C19-
H24N2OCl2P (398.29 g/mol): C, 57.30; H, 6.07; N, 7.03. Found: C,
57.18; H, 6.00; N, 6.96%.
3.3.3. Synthesis of [(Cy2PO)–C7H14N2Cl]Cl (3)
A dry and degassed CH2Cl2 (20 ml) solution of 1-chloro-3-(3-
methylimidazolidin-1-yl)propan-2-ol chloride (1) (0.100 g,
0.47 mmol) under an argon atmosphere was cooled to ꢀ78 °C in
an acetone and dry ice bath. To the cooled solution was added drop-
wise a hexane solution of n-BuLi (0.293 ml, 0.47 mmol). After the
addition, the mixture was stirred at ꢀ78 °C for 1 h and then for an
additional 30 min at room temperature. The reaction solution was
cooled to ꢀ78 °C again and a solution of dicyclohexylchlorophos-
phine (0.112 g, 0.47 mmol) in CH2Cl2 (10 ml) was added dropwise
to the reaction medium. Stirring was continued for a further 1 h at
ꢀ78 °C, then thecooling bath was removedand themixture was stir-
red for 3 h at room temperature. Precipitated lithium chloride was
removed by filtration under argon and then the volatiles were evap-
orated in vacuo to leave a viscous oil of the phosphinite ligand, 3.
Yield 0.183 g, 95.5%; 1H NMR (400.1 MHz, CDCl3, ppm) d: 10.48 (s,
1H, –(CH3)NCHN–), 7.64, 7.45 (2xs, 2H, –NCHCHN–), 4.84 (m, 1H,
NCH2, (a)), 4.53 (m, 1H, NCH2, (b)), 4.16 (br, 1H, –CHOP), 4.10 (s,
3H, NCH3), 3.83 (m, 1H, –CH2Cl, (a)), 3.68 (m, 1H, –CH2Cl, (b)),
1.00–1.95 (m, 22H, protons of P(C6H11)2; 13C NMR (100.6 MHz,
CDCl3, ppm) d: 26.20, 26.27, 26.64, 26.85, 26.98, 27.21 (CH2 of
P(C6H11)2), 36.77 (NCH3), 37.20 (d, 1J = 15.1 Hz, CH of P(C6H11)2),
44.05 (–CH2Cl), 52.34 (NCH2), 77.32 (d, 2J = 22.7 Hz, –CHOP),
123.05, 123.43 (–NCHCHN–), 138.67 (–(CH3)NCHN–); assignment
was based on the 1H–13C HETCOR, DEPT and 1H–1H COSY spectra;
31P–{1H} NMR (162.0 MHz, CDCl3, ppm) d: 148.76 (s, OPCy2); IR,
IR, (KBr, cmꢀ1
) m: 2927, 2851 (aliphatic C–H), 1435 (P–Cy), 1059
(O–P), 520 (Ru–P); Anal. Calc. for C25H42N2OCl4PRu (660.48 g/
mol): C, 45.46; H, 6.41; N, 4.24. Found: C, 45.38; H, 6.30; N, 4.16%.
3.3.6. Synthesis of [Ru((Ph2PO)–C7H14N2Cl)(
[Ru( -Cl)Cl]2 (0.077 g, 0.13 mmol) and [(Ph2-
6-p-cymene)(
g
6-p-cymene)Cl2]Cl (6)
g
l
PO)–C7H14N2Cl]Cl (2) (0.100 g, 0.25 mmol) were dissolved in
25 mL of dry CH2Cl2 under an argon atmosphere and stirred for
30 min at room temperature. The volume of the solvent was then
reduced to 0.5 mL before addition of petroleum ether (10 mL).
The precipitated product was filtered and dried in vacuo yielding
6 as a clear red solid. Yield 0.162 g, 91.6%; M.p.: 110–112 °C. 1H
NMR (400.1 MHz, CDCl3, ppm) d: 9.53 (s, 1H, –(CH3)NCHN–),
7.14–7.93 (m, 12H, P(C6H5)2 + –NCHCHN–), 5.43 (br, 2H, aromatic
protons of p-cymene), 5.23 (br, 2H, aromatic protons of p-cymene),
4.81 (br, 1H, –CHOP), 4.61 (br, 1H, NCH2, (a)), 4.48 (br, 1H, NCH2,
(b)), 3.94 (s, 3H, NCH3), 3.42 (br, 2H, –CH2Cl), 2.46 (m, 1H, CH of
p-cymene), 1.83 (s, 3H, CH3Ph of p-cymene), 0.99 (d, 6H,
3J = 6.8 Hz, (CH3)2CHPh of p-cymene); 13C NMR (100.6 MHz, CDCl3,
ppm) d: 17.22 (CH3Ph of p-cymene), 22.16, 22.23 ((CH3)2CHPh of
(KBr, cmꢀ1
) m: 2923, 2850 (aliphatic C–H), 1446 (P–Cy), 1059
(O–P); Anal. Calc. for C19H36N2OCl2P (410.39 g/mol): C, 55.61; H,
8.84; N, 6.83. Found: C, 55.56; H, 8.71; N, 6.70%.
p-cymene), 30.01 (CH of p-cymene), 37.36 (NCH3), 44.57 (CH2Cl),
2
3.3.4. Synthesis of [Ru((Ph2PO)–C7H14N2Cl)(
g
6-benzene)Cl2]Cl (4)
50.92 (NCH2), 75.11 (d, 2J = 22.9 Hz, –CHOP), 86.77 (d, J31P–13C
=
=
2
[Ru( -Cl)Cl]2 (0.063 g, 0.13 mmol) and [(Ph2PO)–
g
6-benzene)(
l
5.0 Hz, aromatic carbons of p-cymene), 88.89 (d, J31P–13C
2
C7H14N2Cl]Cl (2) (0.100 g, 0.25 mmol) were dissolved in 25 mL of
dry CH2Cl2 under an argon atmosphere and stirred for 30 min at
room temperature. The volume of the solvent was then reduced
to 0.5 mL before addition of petroleum ether (10 mL). The precipi-
tated product was filtered and dried in vacuo yielding 4 as a dark
red solid. Yield 0.150 g, 92.1%; M.p.: 159–161 °C; 1H NMR
(400.1 MHz, DMSO-d6, ppm) d: 8.95 (s, 1H, –(CH3)NCHN–), 7.44–
7.88 (m, 12H, P(C6H5)2 + –NCHCHN–), 5.55 (s, 6H, aromatic protons
of benzene), 5.11 (br, 1H, –CHOP), 4.37 (m, 2H, NCH2), 3.82 (s, 3H,
NCH3), 3.50 (br, 2H, –CH2Cl); 13C NMR (100.6 MHz, DMSO-d6, ppm)
d: 36.29 (NCH3), 44.84 (–CH2Cl), 52.56 (NCH2), 74.96 (d,
2J = 23.2 Hz, –CHOP), 88.10 (aromatic carbons of benzene),
123.54, 123.82 (–NCHCHN–), 128.76 (d, 3J31P–13C = 9.4 Hz,
7.0 Hz, aromatic carbons of p-cymene), 89.35 (d, J31P–13C = 4.0
Hz, aromatic carbons of p-cymene), 92.56 (d, 2J31P–13C = 6.0 Hz, aro-
matic carbons of p-cymene), 96.31, 111.15 (quaternary carbons of
3
p-cymene), 122.60, 123.17 (–NCHCHN–), 128.34 (d, J31P–13C
=
4
10.1 Hz, m-P(C6H5)2)), 131.91 (d, J31P–13C = 6.1 Hz, p-P(C6H5)2),
2
1
133.84 (d, J31P–13C = 12.6 Hz, o-P(C6H5)2), 137.87 (d, J31P–13C
=
52.3 Hz, i-P(C6H5)2), 139.70 (–(CH3)NCHN–); assignment was
based on the 1H–13C HETCOR, DEPT and 1H–1H COSY spectra;
31P–{1H} NMR (162.0 MHz, CDCl3, ppm) d: 124.23 (s, Ru–OPPh2);
IR, (KBr, cmꢀ1
) m: 3053 (aromatic C–H), 1435 (P–Ph), 1047 (O–P),
532 (Ru–P); Anal. Calc. for C29H38N2OCl4PRu (704.49 g/mol): C,
49.44; H, 5.44; N, 3.98. Found: C, 49.34; H, 5.32; N, 3.89%.
4
m-P(C6H5)2), 132.98 (d, J31P–13C = 3.0 Hz, p-P(C6H5)2), 133.52 (d,
3.3.7. Synthesis of [Ru((Cy2PO)–C7H14N2Cl)(
[Ru( -Cl)Cl]2 (0.075 g, 0.12 mmol) and [(Cy2
6-p-cymene)(
g
6-p-cymene)Cl2]Cl (7)
2J31P–13C = 20.1, o-P(C6H5)2)), 137.10 (–(CH3)NCHN–), 139.49 (d,
1J31P–13C = 52.3 Hz, i-P(C6H5)2); assignment was based on the
1H–13C HETCOR, DEPT and 1H–1H COSY spectra; 31P–{1H} NMR
(162.0 MHz, DMSO-d6, ppm) d: 97.68; (CDCl3, ppm) d: 127.82 (s,
g
l
PO)–C7H14N2Cl]Cl (3) (0.100 g, 0.24 mmol) were dissolved in
25 mL of dry CH2Cl2 under an argon atmosphere and stirred for
30 min at room temperature. The volume of the solvent was then
reduced to 0.5 mL before addition of petroleum ether (10 mL).
The precipitated product was filtered and dried in vacuo yielding
Ru–OPPh2); IR, (KBr, cmꢀ1
1047 (O–P), 532 (Ru–P); Anal. Calc. for
)
m: 3064 (aromatic C–H), 1435 (P–Ph),
C25H30N2OCl4PRu

254
M. Aydemir et al. / Polyhedron 81 (2014) 245–255
7 as a clear red solid. Yield 0.163 g, 93.3%; M.p.: 106–108 °C. 1H
NMR (400.1 MHz, CDCl3, ppm) d: 9.81 (s, 1H, –(CH3)NCHN–),
7.66, 7.08 (2xs, 2H, –NCHCHN–), 5.64 (d, 2H, 3J = 3.8 Hz, aromatic
protons of p-cymene), 5.61 (d, 2H, 3J = 3.8 Hz, aromatic protons of
p-cymene), 5.35 (m, 1H, –CHOP), 4.72 (m, 1H, NCH2, (a)), 4.43
(m, 1H, NCH2, (b)), 4.02 (s, 3H, NCH3), 3.83 (m, 1H, –CH2Cl, (a)),
3.26 (m, 1H, –CH2Cl, (b)), 2.81 (m, 1H, –CH of p-cymene), 2.12 (s,
3H, CH3Ph of p-cymene), 1.28–1.36 (m, 22H, P(C6H11)2), 0.87 (d,
6H, 3J = 6.5 Hz, (CH3)2CHPh of p-cymene); 13C NMR (100.6 MHz,
CDCl3, ppm) d: 18.77 (CH3Ph of p-cymene), 22.33, 22.48 ((CH3)2
CHPh of p-cymene), 26.25, 26.94, 27.21, 27.85, 28.48, 29.06 (CH2
of P(C6H11)2), 30.83 (CH of p-cymene), 37.38 (NCH3), 46.06
(–CH2Cl), 46.35 (d, 1J = 29.7 Hz, CH of P(C6H11)2), 49.79 (NCH2),
74.50 (d, 2J = 24.2 Hz, –CHOP), 84.86, 90.33 (aromatic carbons of
p-cymene), 96.28, 110.99 (quaternary carbons of p-cymene),
122.40, 122.42 (–NCHCHN–), 139.09 (–(CH3)NCHN–); assignment
was based on the 1H–13C HETCOR, DEPT and 1H–1H COSY spectra;
31P–{1H} NMR (162.0 MHz, CDCl3, ppm) d: 154.25 (s, Ru–OPCy2);
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.poly.2014.05.079.
References
[1] T. Welton, Chem. Rev. 99 (1999) 2071.
[2] K.R. Seddon, J. Chem. Technol. Biotechnol. 68 (1997) 351.
[3] Y. Chauvin, H. Olivier-Bourbigou, ChemTech 25 (1995) 26.
[4] R.T. Carlin, J.S. Wilkes, in: G. Mamantov, A. Popov (Eds.), Advances in Non-
aqueous Chemistry, VCH, New York, 1994.
[5] M. Freemantle, Chem. Eng. News 15 (2000) 37. and 4 (1999) 23.
[6] H. Carmichael, Chem. Br. 1 (2000) 36.
[7] S.V. Malhotra, H. Zhao, Phys. Chem. Liq. 42 (2004) 215.
[8] Y. Xiao, S.V. Malhotra, J. Organomet. Chem. 690 (2005) 3609.
[9] P. Nockemann, M. Pellens, K. Van Hecke, L. Van Meervelt, J. Wouters, B. Thijs, E.
Vanecht, T.N. Parac-Vogt, H. Mehdi, S. Schaltin, J. Fransaer, S. Zahn, B. Kirchner,
K. Binnemans, Chem. Eur. J. 16 (2010) 1849.
[10] C. Chiappe, C.S. Pomelli, U. Bardi, S. Caporali, Phys. Chem. Chem. Phys. 14
(2012) 5045.
IR, (KBr, cmꢀ1
) m: 2926, 2852 (aliphatic C–H), 1446 (P–Cy), 1057
[11] (a) T. Welton, Coord. Chem. Rev. 248 (2004) 2459;
(b) J.P. Hallett, T. Welton, Chem. Rev. 111 (2011) 3508.
[12] J.P. Hallett, T. Welton, Chem. Rev. 111 (2011) 3508.
[13] A. Corma, H. Garcia, A. Leyva, Tetrahedron 60 (2004) 8553.
[14] S. Lee, Y.J. Zhang, J.Y. Piao, H. Yoon, C.E. Song, J.H. Choi, J. Hong, Chem.
Commun. (2003) 2624.
[15] T.J. Geldbach, P.J. Dyson, J. Am. Chem. Commun. 126 (2004) 8114.
[16] C. Baleizao, B. Gigante, H. Garcia, A. Corma, Tetrahedron Lett. 44 (2003) 6813.
[17] M.D. Rudd, M.A. Creighton, J.A. Kautz, Polyhedron 23 (2004) 1923.
[18] K.G. Gaw, M.B. Smith, J.W. Steed, J. Organomet. Chem. 664 (2002) 294.
[19] F. Agbossou, J.-F. Carpentier, F. Hopiot, I. Suisse, A. Mortreux, Coord. Chem. Rev.
178–180 (1998) 1615.
[20] H.J. Kreuzfelt, C. Döbler, J. Mol. Catal. A 136 (1998) 105.
[21] F. Agbossou-Niedercorn, I. Suisse, Coord. Chem. Rev. 242 (2003) 145.
[22] P. Bergamini, V. Bertolasi, F. Milani, Eur. J. Inorg. Chem. (2004) 1277.
[23] G.D. Cuny, S.L. Buchwald, J. Am. Chem. Soc. 115 (1993) 2066.
[24] Z. Csok, G. Szalontai, G. Czira, L. Kollar, J. Organomet. Chem. 570 (1998) 23.
[25] R.H. Crabtree, The Organometallic Chemistry of the Transition Metals, Wiley-
Interscience, New York, 2001.
[26] H.B. Kagan, M. Sasaki, Transition Metals for Organic Synthesis, Wiley-VCH,
Weinheim, 1998.
[27] P.W. Galka, H –B. Kraatz, J. Organomet. Chem. 674 (2003) 24.
[28] R.A.W. Johnstone, A.H. Wilby, I.D. Entwistle, Chem. Rev. 85 (1985) 129.
[29] M. Yig˘it, B. Yig˘it, I. Özdemir, E. Çetinkaya, B. Çetinkaya, Appl. Organometal.
Chem. 20 (2006) 322.
[30] R. Noyori, H. Takaya, Acc. Chem. Res. 23 (1990) 345.
[31] S. Ram, R.E. Ehrenkaufer, Synthesis (1988) 91.
[32] O. Pamies, J.-E. Backvall, Chem. Eur. J. 23 (7) (2001) 5052.
[33] R. Noyori, T. Ohkuma, M. Kitamura, H. Takaya, N. Sayo, H. Kumobayashi, S.
Akutagawa, J. Am. Chem. Soc. 109 (1987) 5856.
(O–P), 528 (Ru–P); Anal. Calc. for C29H50N2OCl4PRu (716.58 g/
mol): C, 48.61; H, 7.03; N, 3.91. Found: C, 48.53; H, 6.92; N, 3.83%.
3.4. X-ray diffraction structure analysis
The single crystal data of 1-chloro-3-(3-methylimidazolidin-1-
yl)propan-2-ol chloride (1) were collected using a BRUKER APEX
II CCD detector with graphite crystal monochromated Mo Ka radi-
ation from a K780 X-ray generator applying 50 kV and 40 mA. The
structure was solved by direct methods using SHELXS-97 and refined
against F2 by full matrix least-squares using SHELXL-97 [90]. The
X-ray diffraction study of the crystal reveals that it belongs to
monoclinic system with space group P2(1). The dimensions of
the unit cell can be denoted as 4.90220 Å for (a), 14.1086 Å for
(b), 7.29760 Å for (c). Hydrogen atoms attached to carbon were
placed in calculated positions. Anisotropic displacement parame-
ters, which were applied to all non-hydrogen atoms, were refined.
The crystal data of the structure are given in Table 1. The molecular
drawings of 1 were obtained with Mercury 3.0. The acquired
results of the X-ray structure determination are presented in
Tables 1 and 2 and Figs. 1 and 2.
[34] T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 117
(1995) 2675.
[35] A. Kilic, F. Durap, M. Aydemir, A. Baysal, E. Tasß, J. Organomet. Chem. 693 (2008)
4. Conclusion and perspectives
2835.
[36] H. Shimizu, I. Nagasaki, T. Satio, Tetrahedron 61 (2005) 5405.
[37] M. Aydemir, F. Durap, A. Baysal, N. Meric, A. Buldag˘, B. Gümgüm, S. Özkar, L.T.
Yıldırım, J. Mol. Catal. A 326 (2010) 75.
In this work, the preparation of four new Ru(II)–arene com-
plexes based on ionic liquid phosphinite ligands is reported for
the first time. These complexes have also exhibited promising cat-
alytic activity in the transfer hydrogenation reaction of ketones in
2-propanol. Furthermore, the influences of arene rings and alkyl
groups on the phosphorus atom in the catalytic transfer hydroge-
nation of aromatic ketones were also examined, and it was seen
that the catalytic activities depend on the groups (phenyl and
cyclohexyl) on the phosphorus atom, while they are independent
on the arene moieties bound to metal center. Further studies of
other transition metal complexes of this ligand are in progress
and will be reported in due course.
[38] M. Aydemir, A. Baysal, N. Meric, B. Gümgüm, J. Organomet. Chem. 694 (2009)
2488.
[39] M. Aydemir, N. Meric, A. Baysal, Y. Turgut, C. Kayan, S. Seker, M. Tog˘rul, B.
Gümgüm, J. Organomet. Chem. 696 (2011) 1541.
[40] A. Baysal, M. Aydemir, F. Durap, B. Gümgüm, S. Özkar, L.T. Yıldırım, Polyhedron
26 (2007) 3373.
[41] M. Aydemir, A. Baysal, F. Durap, B. Gümgüm, S. Özkar, L.T. Yıldırım, Appl.
Organomet. Chem. 23 (11) (2009) 467.
[42] M.S. Balakrishna, R. McDonald, Inorg. Chem. Commun. 5 (2002) 782.
[43] P. Bergamini, V. Bertolasi, M. Cattabriga, V. Ferretti, U. Loprieno, N. Mantovani,
L. Marvelli, Eur. J. Inorg. Chem. (2003) 918.
[44] R. Ceron-Camacho, V. Gomez-Benitez, R. Le Lagadec, D. Morales-Morales, R.A.
Toscano, J. Mol. Catal. A 247 (2006) 124.
[45] I.D. Kostas, Inorg. Chim. Acta 355 (2003) 424.
[46] E.A. Broger, W. Burkart, M. Hennig, M. Scalone, R. Schmid, Tetrahedron
Asymmetry 9 (1998) 4043.
[47] E. Hauptman, R. Shapiro, W. Marshall, Organometallics 17 (1998) 4976.
[48] K. Ruhlan, P. Gigler, E. Herdweck, J. Organomet. Chem. 693 (2008) 874.
[49] M. Hariharasarma, C.H. Lake, C.L. Watkins, M.G. Gray, J. Organomet. Chem. 580
(1999) 328.
[50] G. Esquius, J. Pons, R. Yanez, J. Ros, R. Mathieu, N. Lugan, B. Donnadieu, J.
Organomet. Chem. 667 (2003) 126.
[51] Z. Fei, R. Scopelliti, P.J. Dyson, Inorg. Chem. 42 (2003) 2125.
[52] Z. Fei, R. Scopelliti, P.J. Dyson, Eur. J. Inorg. Chem. (2004) 530.
[53] H. Le Bozec, D. Touchard, P.H. Dixneuf, Adv. Organomet. Chem. 29 (1989) 163.
Acknowledgements
Partial support of this work by The Scientific and Technological
Research Council of Turkey and Dicle University Research Fund
(Project number: DÜAPK 05-FF-27), and the analysis conducted
by Dicle University Science Faculty and Technology Research
Center (DUBTAM) are gratefully acknowledged.

M. Aydemir et al. / Polyhedron 81 (2014) 245–255
255
[54] A.M. Maj, K.M. Pietrusiewicz, I. Suisse, F. Agbossou, A. Mortreux, Tetrahedron
[72] M.J. Palmer, M. Will, Tetrahedron Asymmetry 10 (1999) 2045.
[73] E.P. Kelson, P.P. Phengsy, J. Chem. Soc., Dalton Trans. (2000) 4023.
Asymmetry 10 (1999) 831.
[55] F. Majoumo, P. Lönnecke, O. Kühl, E. Hey-Hawkins, Z. Anorg. Allg. Chem. 630
(2004) 305.
[74] H. Zhang, B.C. Yang, Y.Y. Li, Z.R. Donga, J.X. Gao, H. Nakamura, K. Murata, T.
Ikariya, Chem. Commun. (2003) 142.
[56] M.A. Bennet, G.B. Robertson, A.K. Smith, J. Organomet. Chem. 43 (1972) C41.
[57] H. Yang, N. Lugan, R. Mathieu, Ann. Quim. Int. Ed. 93 (1997) 28.
[58] R. Tribo, S. Munoz, J. Pons, R. Yanez, A. Alvarez-Larena, J.F. Piniella, J. Ros, J.
Organomet. Chem. 690 (2005) 4072.
[75] J. Hannedouche, G.J. Clarkson, M. Wills, J. Am. Chem. Soc. 126 (2004) 986.
[76] J.W. Faller, A.R. Lavoie, Organometallics 20 (2001) 5245.
[77] P. Pelagatti, M. Carcelli, F. Calbiani, C. Cassi, L. Elviri, C. Pelizzi, U. Rizzotti, D.
Rogolino, Organometallics 24 (2005) 5836.
[59] E. de la Encarnacion, J. Pons, R. Yanez, J. Ros, Inorg. Chim. Acta 358 (2005)
3272.
[60] I. Moldes, E. de la Encarnacion, J. Ros, A. Alvarez-Larena, J.F. Piniella, J.
Organomet. Chem. 566 (1998) 165.
[78] C. Standfest-Hauser, C. Slugovc, K. Mereiter, R. Schmid, K. Kirchner, L. Xiao, W.
Weissensteiner, J. Chem. Soc., Dalton Trans. (2001) 2989.
[79] A.M. Maj, K.M. Pietrusiewicz, I. Suisse, F. Agbossou, A. Mortreux, J. Organomet.
Chem. 626 (2001) 157.
[61] P.Le Gendre, M. Offenbecher, C. Bruneau, P.H. Dixneuf, Tetrahedron
Asymmetry 9 (1998) 2279.
[80] K.-J. Haack, S. Hashiguchi, A. Fuji, T. Ikariya, R. Noyori, Angew. Chem. Int. Ed.
Engl. 36 (1997) 285.
[62] Q. Zhang, G. Hua, P. Bhattacharrya, A.M.Z. Slawin, J.D. Woollins, J. Chem. Soc.,
Dalton Trans. (2003) 3250.
[63] M. Alvarez, N. Lugan, R. Mathieu, J. Chem. Soc., Dalton Trans. (1994) 2755.
[64] H. Yang, M. Alvarez, N. Lugan, R. Mathieu, J. Chem. Soc., Chem. Commun.
(1995) 1721.
[65] G. Venkatachalam, R. Ramesh, Inorg. Chem. Commun. 8 (2005) 1009.
[66] M. Aydemir, A. Baysal, N. Meric, C. Kayan, M. Tog˘rul, B, Gümgüm, Appl.
Organomet. Chem. 24 (2010) 215.
[81] A. Caballero, F.A. Jalon, B.R. Manzano, G. Espino, M. Perez-Manrique, A.
Mucientes, F.J. Poblete, M. Maestro, Organometallics 23 (2004) 5694.
[82] P. Dani, T. Karlen, R.A. Gossage, S. Gladialli, G. van Koten, Angew. Chem. Int. Ed.
Engl. 39 (2000) 743.
[83] J.-X. Gao, X.-D. Yi, P.-P. Xu, C.-L. Tang, H.-L. Wan, T. Ikariya, J. Organomet.
Chem. 592 (1999) 290.
[84] J.-X. Gao, H. Zhang, X.-D. Yi, P.-P. Xu, C.-L. Tang, H.-L. Wan, K.-R. Tsai, T. Ikariya,
Chirality 12 (2000) 383.
[67] F. Durap, M. Aydemir, D. Elma, A. Baysal, Y. Turgut, C. R. Chimie 16 (2013) 363.
[68] M. Aydemir, F. Durap, C. Kayan, A. Baysal, Y. Turgut, Synlett 23 (2012) 2777.
[69] M. Aydemir, N. Meric, F. Durap, A. Baysal, M. Tog˘rul, J. Organomet. Chem. 695
(2010) 1392.
[85] J.-S. Chen, Y.-Y. Li, Z.-R. Dong, B.-Z. Li, J.-X. Gao, Tetrahedron Lett. 45 (2004)
8415.
[86] Z.-R. Dong, Y.-Y. Li, J.-S. Chen, B.-Z. Li, Y. Xing, J.-X. Gao, Org. Lett. 7 (2005)
1043.
[70] M. Aydemir, N. Meric, A. Baysal, B. Gümgüm, M. Tog˘rul, Y. Turgut, Tetrahedron
[87] M.A. Bennet, A.K. Smith, J. Chem. Soc., Dalton Trans. (1974) 233.
[88] M.A. Bennet, T.N. Huang, T.W. Matheson, A.K. Smith, Inorg. Synth. 7 (1982) 74.
[89] R.A. Zelonka, M.C. Baird, J. Organomet. Chem. 35 (1972) C43.
[90] G.M. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112.
Asymmetry 21 (2010) 703.
[71] E.L. Muetterties, J.R. Bleeke, E.J. Wucherer, T.A. Albright, Chem. Rev. 82 (1982)
499.