Organometallic ruthenium, rhodium and iridium complexes containing a P-bound thiophene-2-(N-diphenylphosphino)methylamine ligand: Synthesis, molecular structure and catalytic activity

Article abstract of DOI:10.1016/j.jorganchem.2011.03.043

Reaction of Ph₂PNHCH₂-C₄H₃S with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂, [Ru(η⁶-benzene)(μ-Cl)Cl]₂, [Rh(μ-Cl)(cod)] ₂ and [Ir(η⁵-C₅Me₅)(μ-Cl)Cl] ₂ yields complexes [Ru(Ph₂PNHCH₂-C ₄H₃S)(η⁶-p-cymene)Cl₂], 1, [Ru(Ph₂PNHCH₂-C₄H₃S) (η⁶-benzene)Cl₂], 2, [Rh(Ph₂PNHCH ₂-C₄H₃S)(cod)Cl], 3 and [Ir(Ph ₂PNHCH₂-C₄H₃S)(η⁵- C₅Me₅)Cl₂], 4, respectively. All complexes were isolated from the reaction solution and fully characterized by analytical and spectroscopic methods. The structure of [Ru(Ph₂PNHCH ₂-C₄H₃S)(η⁶-benzene)Cl ₂], 2 was also determined by single crystal X-ray diffraction. 1-4 are suitable precursors forming highly active catalyst in the transfer hydrogenation of a variety of simple ketones. Notably, the catalysts obtained by using the ruthenium complexes [Ru(Ph₂PNHCH₂-C ₄H₃S)(η⁶-p-cymene)Cl₂], 1 and [Ru(Ph₂PNHCH₂-C₄H₃S) (η⁶-benzene)Cl₂], 2 are much more active in the transfer hydrogenation converting the carbonyls to the corresponding alcohols in 98-99% yields (TOF ≤ 200 h^-1) in comparison to analogous rhodium and iridium complexes.

Full text of DOI:10.1016/j.jorganchem.2011.03.043

Journal of Organometallic Chemistry 696 (2011) 2584e2588
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Organometallic ruthenium, rhodium and iridium complexes containing a P-bound
thiophene-2-(N-diphenylphosphino)methylamine ligand: Synthesis, molecular
structure and catalytic activity
,
a
a
a
b
Murat Aydemir a, Akın Baysal a , Nermin Meric , Cezmi Kayan , Bahattin Gümgüm , Saim Özkar ,
*
Ertan S¸ ahin c
a Dicle University, Department of Chemistry, 21280 Diyarbakır, Turkey
b Middle East Technical University, Department of Chemistry, 06531 Ankara, Turkey
c Atatürk University, Department of Chemistry, 25240 Erzurum, Turkey
a r t i c l e i n f o
a b s t r a c t
6-p-cymene)(
m
-Cl)Cl]2, [Ru(
h
6-benzene)(
6-p-cymene)Cl2], 1,
and [Ir(Ph2PNHCH2-
5-C5Me5)Cl2], 4, respectively. All complexes were isolated from the reaction solution and fully
characterized by analytical and spectroscopic methods. The structure of [Ru(Ph2PNHCH2-C4H3S)(h6
m-Cl)Cl]2, [Rh(m-
Article history:
Reaction of Ph2PNHCH2-C4H3S with [Ru(
h
Cl)(cod)]2 and [Ir(
[Ru(Ph2PNHCH2-C4H3S)(
C4H3S)(
h
5-C5Me5)(
m
-Cl)Cl]2 yields complexes [Ru(Ph2PNHCH2-C4H3S)(
h
Received 9 February 2011
Received in revised form
21 March 2011
h
6-benzene)Cl2], 2, [Rh(Ph2PNHCH2-C4H3S)(cod)Cl],
3
h
Accepted 29 March 2011
-
benzene)Cl2], 2 was also determined by single crystal X-ray diffraction. 1e4 are suitable precursors
Keywords:
forming highly active catalyst in the transfer hydrogenation of a variety of simple ketones. Notably, the
Aminophosphine
Transfer hydrogenation
Ruthenium
Rhodium
Iridium
catalysts obtained by using the ruthenium complexes [Ru(Ph2PNHCH2-C4H3S)(h
6-p-cymene)Cl2], 1 and
[Ru(Ph2PNHCH2-C4H3S)(h
6-benzene)Cl2], 2 are much more active in the transfer hydrogenation con-
verting the carbonyls to the corresponding alcohols in 98e99% yields (TOF ꢀ 200 hꢁ1) in comparison to
analogous rhodium and iridium complexes.
X-ray diffraction
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
hydrogenation of ketones by 2-propanol is convenient in large-
scale synthesis since there is no need to employ a high hydrogen
Aminophosphines and bis(phosphino)amines with PeNH and
PeNeP skeletons, respectively, have been used as versatile ligands,
and varying the substituents on both the P- and N-centers gives rise
the changes in the PeNeP angle and the conformation around the
P-centers [1]. Small variations in these ligands can cause significant
changes in their coordination behavior and the structural features
of the resulting complexes [2]. A large number of complexes with
aminophosphine ligands have been employed in different catalytic
reactions including allylic alkylation [3], amination [4], Heck [5]
Sonogashira [6], Suzuki [7], hydroformylation [8] and hydrogena-
tion [9]. Some aminophosphines and their derivatives have also
found application as anticancer drugs [10], herbicides and antimi-
crobial agents, as well as neuroactive agents [11].
pressure or to use hazardous reducing agents [13]. Although very
frequently ruthenium-based catalysts have been applied in the
enantioselective hydrogenation of prochiral ketones [14e16],
rhodium or iridium complexes have also been employed and found
to be an efficient catalyst in some processes along with potential
industrial applications [17,18]. Today, the asymmetric transfer
hydrogenation [19e21] of prochiral ketones is one of the most
attractive methods for synthesizing optically active secondary
alcohols, which form an important class of intermediates for fine
chemicals and pharmaceuticals [22].
As part of our continuing research program on the amino-
phosphine complexes we report here the synthesis of new ruthe-
nium, rhodium and iridium complexes of Ph2PNHCH2-C4H3S. All
the new complexes were isolated from the reaction solution and
fully characterized by analytical and spectroscopic methods. Our
report includes also the X-ray crystal structure of [Ru(Ph2PNHCH2-
Transition-metal-catalyzed transfer hydrogenation of a wide
variety of functional groups by different hydrogen donors is an
interesting alternative to conventional hydrogenation [12]. Transfer
C4H3S)(h
6-benzene)Cl2] and pertinent features of this structure. In
addition, metal complexes of this aminophosphine were tested as
catalyst in the transfer hydrogenation of a variety of simple alkyl
ketones.
* Corresponding author. Tel.: þ90 412 248 8550; fax: þ90 412 248 8300.
E-mail address: akinb@dicle.edu.tr (A. Baysal).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.03.043

M. Aydemir et al. / Journal of Organometallic Chemistry 696 (2011) 2584e2588
2585
Scheme 1. The formation of complexes [Ru(Ph2PNHCH2-C4H3S)(
[Ir(Ph2PNHCH2-C4H3S)(
5-C5Me5)Cl2], 4 from the reaction of Ph2PNHCH2-C4H3S and (i) 1/2 equiv. [Ru(
[Rh( -Cl)(cod)]2, (iv) 1/2 equiv. [Ir( -Cl)Cl]2, all in tetrahydrofuran.
5-C5Me5)(
h
6-p-cymene)Cl2], 1, [Ru(Ph2PNHCH2-C4H3S)(
h
6-benzene)Cl2],
2
[Rh(Ph2PNHCH2-C4H3S)(cod)Cl],
3 and
h
h
6-p-cymene(
m-Cl)Cl]2, (ii) 1/2 equiv. [Ru(
h
6-benzene)(
m
-Cl)Cl]2, (iii) 1/2 equiv.
m
h
m
2. Result and discussion
2.1. Synthesis of the complexes
similar to those of dichloro(h
6-p-cymene)(triphenylphosphine)-
ruthenium(II)complex [27], which has the same classic pseudo-
tetrahedral piano-stool structure.
In previously reported structures [28e30],
a trans bond
Reaction of Ph2PNHCH2-C4H3S with [Ru(
[Ru( -Cl)Cl]2, [Rh( -Cl)(cod)]2 and [Ir(
6-benzene)(
Cl]2 yields new complexes [Ru(Ph2PNHCH2-C4H3S)(
Cl2], 1, [Ru(Ph2PNHCH2-C4H3S)(
6-benzene)Cl2], 2, [Rh(Ph2PNHCH2-
C4H3S)(cod)Cl], and [Ir(Ph2PNHCH2-C4H3S)(
5-C5Me5)Cl2], 4,
h
6-p-cymene)(
5-C5Me5)(
6-p-cymene)
m
-Cl)Cl]2,
lengthening has been observed in the Ru-C bonds trans to P donors
such as PPh3. In the case of 2 with C1/C2 trans to P, the RueC1 and
RueC2 bonds are longer than the other RueC bonds. A comparison
of the PeRueCl1 (84.6(2)), PeRueCl2 (88.1(3)) and Cl1eRueCl2
h
m
m
h
m-Cl)
h
h
3
h
(88.1(2)) angles reveals that (h
6-benzene) group has similar steric
respectively, asshowninScheme1. Thecomplexeswereisolatedfrom
the reaction solution as analytically pure substances and character-
ized by analytical and spectroscopic techniques following the
procedures described elsewhere [23,24]. Some pertinent chemical
shifts for 1H and 31P NMR, as well as coupling constants, of
compounds 1e4 are summarized in Table 1.
hindrance; i.e., the benzene ring is almost parallel to the plane of P,
Cl1 and Cl2. No meaningful interactions between independent
complexes are observed in the crystal packing (Fig. 2), the Cl/HeC
distances ranging from 3.495 to 3.767 Å.
In summary, the 2-thiophenemethylamine phosphine, h6
-
benzene, and two chloro ligands affords a classical pseudo-
octahedral ruthenium(II) complex with typical RueP/RueCl bond
lengths and angles.
As part of the characterization of the complexes we report
herein the crystal structure of one representative example, namely
complex 2. Single crystals suitable for X-ray diffraction study were
obtained by slow diffusion of diethyl ether into a solution of the
compound in dichloromethane over several days. The single crystal
X-ray structure analysis of [Ru(Ph2PNHCH2-C4H3S)(h
6-benzene)
Cl2], 2 reveals a typical piano-stool geometry with the ruthenium
atom being coordinated by a benzene, 2-thiophenemethylamine
phosphine and two chloro ligands as shown in Fig. 1.
The distance between Ru and the centroid of the
p-bonded
benzene moiety is 1.698 (8) Å and the mean value of the RueC bond
distances is 2.192 (19) Å. These dimensions agree well with those of
the several related complexes, e.g. [CpRu(PPh3)2(NCCH3)]BF4 [25]
or [CpRu(PPh3)2(NCPh)]PF6 [26]. Also bond lengths and angles in
the compound 2 (see Table 2 and Supplementary materials) are
Table 1
Selected NMR data for complexes 1e4.
Complexes
d
(1H)
d(
31P)
CH2
NH
Aromatics (Ph)
1
2
3
4
3.81(dd, J 6.4; 6.8 Hz)
3.88(dd, J 6.2; 6.4 Hz)
3.98(dd, J 5.2; 6.8 Hz)
3.94(dd, J 5.8; 6.4 Hz)
3.58 (m)
3.56 (m)
4.33 (m)
3.12 (m)
7.53e7.97
7.46e7.96
7.42e7.99
7.42e7.95
61.0
61.7
60.6a
34.1
Fig. 1. Perspective view of the complex [Ru(Ph2PNHCH2-C4H3S)(
the atom numbering scheme. Displacement ellipsoids are at the 50% probability level.
h
6-benzene)Cl2] (2)with
a
1J(103Rh ꢁ 31P) ¼ 158.8 Hz.

2586
M. Aydemir et al. / Journal of Organometallic Chemistry 696 (2011) 2584e2588
Table 2
Table 3
Selected bond lengths (Å) and angles (ꢂ) for (2).
Transfer hydrogenation of various simple ketones with iso-PrOH catalyzed by
[Ru(Ph2PNHCH2-C4H3S)(
6-p-cymene)Cl2], 1, [Ru(Ph2PNHCH2-C4H3S)( 6-benzene)
5-C5Me5)
h
h
Bond lengths
RueP
PeC(12)
SeC(20)
RueCl1
RueC(6)
RueC(2)
Bond angles
RuePeN
RuePeC(13)
NePeC(13)
Cl(1)eRueCl(2)
Cl(1)eRueP
Cl2], 2, [Rh(Ph2PNHCH2-C4H3S)(cod)Cl], 3 and [Ir(Ph2PNHCH2-C4H3S)(
Cl2], 4a.
h
2.328(1)
1.817(4)
1.693(4)
2.410(2)
2.176(3)
2.260(3)
PeN
1.654(3)
1.827(4)
1.699(6)
2.413(2)
2.256(2)
PeC(13)
SeC(23)
RueCl2
RueC(1)
Cat
Substrate
Product
Time
Conversion(%)b
TOF(h-1)c
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
O
OH
30 min
30 min
2 h
97
98
99
98
98
97
98
99
99
98
98
99
99
98
98
97
194
196
50
2 h
49
111.4(1)
115.9(2)
105.9(2)
88.1(2)
RuePeC(12)
NePeC(12)
C(12)ePeC(13)
112.8(2)
104.8(2)
105.2(2)
30 min
30 min
2 h
2 h
2 h
2 h
3 h
3 h
4 h
196
194
49
50
50
49
33
33
25
O
OH
84.6(2)
Cl(2)eRueP
88.1(3)
O
OH
2.2. Catalytic transfer hydrogenation of ketones
The activity of Ru(II)-arene complexes is well known in the
catalytic transfer hydrogenation of carbonyl compounds [31e33].
Complexes with sp3-hybribized nitrogens and containing NeH
bonds exhibit high catalytic activity. On the other hand, the pres-
ence of an NeH groups in the ligands possibly stabilizes a six
membered ring, which is formed as transient by hydrogen bonding
with the oxygen atom of ketone [34e37]. Hence, these kinds of
ligands are attractive and also widely used in ruthenium, rhodium
and iridium complexes for catalytic hydrogenations reactions
[38,39]. Recently, we have reported that the novel half-sandwich
complexes, based on the ligands with PeN and PeO backbone,
are active catalysts in the reduction of aromatic ketones [40,41].
As part of our continuing research in this area [42e44], we
report herein the results of catalytic activity tests using the
complexes 1e4 in the transfer hydrogenation of a variety of simple
alkyl ketones to the corresponding alcohols in iso-PrOH solution. In
a typical experiment, 0.01 mmol of the complex and 1.0 mmol of
ketone were added to a solution of NaOH in iso-PrOH (0.05 mmol of
NaOH in 10 mL iso-PrOH) and refluxed at 82 ꢂC. The reaction was
O
OH
4 h
7 h
7 h
25
14
14
a
Refluxing in iso-PrOH; acetophenone/Ru/NaOH, 100:1:5.
Determined by GC (three independent catalytic experiments).
b
c
Referred at the reaction time indicated in column; TOF ¼ (mol product/mol
Ru(II)Cat.) ꢃ hꢁ1
.
followed by using GC. For alkyl ketones, heating is generally
required to achieve high conversion. With a complex/NaOH ratio of
1/5, the complexes are highly active leading to a quantitative
transformation of the ketone, with a moderate TOF. The results of
catalytic tests are listed in Table 3.
It is noteworthy that the complexes 1, 2, 3 and 4 display the
different activity, when used with a complex/NaOH ratio of 1/5.
Complexes 1 and 2 are the most active catalysts leading to quan-
titative transformation of ketones to the corresponding alcohol
with a moderate TOF value of 200 hꢁ1. It should be pointed out that
complexes 1 and 2 are more active catalysts than the corresponding
Fig. 2. Crystal packing of [Ru(Ph2PNHCH2-C4H3S)(h
6-benzene)Cl2], 2.

M. Aydemir et al. / Journal of Organometallic Chemistry 696 (2011) 2584e2588
2587
spectra were recorded as KBr pellet in the range 4000e400 cmꢁ1
Table 4
on
a
Mattson 1000 ATI UNICAM FT-IR spectrometer. 1H
Crystal data and structure refinement for (2).
(400.1 MHz), 13C NMR (100.6 MHz) and 31P-{1H} NMR (162.0 MHz)
spectra were recorded on a Bruker Avance 400 spectrometer, with
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
C23H22NPCl2SRu
547.4
293(2) K
0.71073 Å
triclinic
P-1
d
referenced to external TMS and 85% H3PO4, respectively.
Elemental analysis was carried out on a Fisons EA 1108 CHNS-O
instrument. Melting points were recorded on
Model apparatus with open capillaries.
a Gallenkamp
Unit cell dimensions
a ¼ 9.226(6) Å
b ¼ 9.9280(16) Å
c ¼ 12.509(16) Å
1136.13(12) Å3
2
a
b
g
¼ 94.05ꢂ
¼ 96.192(3)ꢂ
¼ 12.509ꢂ
4.2. GC analyses
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
1.60 Mg/m3
GC analyses were performed on an HP 6890N Gas Chromato-
graph equipped with capillary column (5% biphenyl, 95% dime-
1
1.098 mmꢁ
552
thylsiloxane) (30 m ꢃ 0.32 mm ꢃ 0.25
mm). The GC parameters for
Crystal
Crystal size
block:yellow
0.20 ꢃ 0.02 ꢃ 0.02 mm3
2.1e26.4ꢂ
ꢁ11 ꢀ h ꢀ 11, ꢁ11 ꢀ k ꢀ
12, ꢁ15 ꢀ l ꢀ 15
24222
transfer hydrogenation of ketones were as follows; initial temper-
ature, 110 ꢂC; initial time, 1 min; solvent delay, 4.48 min; temper-
ature ramp 80 ꢂC/min; final temperature, 200 ꢂC; final time,
21.13 min; injector port temperature, 200 ꢂC; detector temperature,
q
-range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to
Max. and min. transmission 0.927 and 0.873
200 ꢂC, injection volume, 2.0
mL.
4654 [Rint ¼ 0.039]
q
¼ 30.7ꢂ
99.7%
Refinement method
Full-matrix least-squares on F2
4.3. Transfer hydrogenation of ketones
Data/restraints/parameters
4371/0/264
1.061
Goodness-of-fit on F2
Typical procedure for the catalytic hydrogen transfer reaction:
Final R indices [F2 > 2
R indices (all data)
Extinction coefficient
s
(F2)] R1 ¼ 0.036, wR2 ¼ 0.097
R1 ¼ 0.039, wR2 ¼ 0.101
a
suspension of metal complexes Ru(II), Rh(I) or Ir(III)
(0.005 mmol), NaOH (0.025 mmol) and alkyl ketone (0.5 mmol) in
degassed iso-PrOH (5 mL) was refluxed until the reaction is
completed. After this time a sample of the reaction mixture is
taken, diluted with acetone and analyzed immediately by GC.
Yields obtained are related to the residual unreacted ketone.
0.0219
0.814 and ꢁ0.710 e Åꢁ
3
Largest diff. peak and hole
precursors: [Ru(
24 h) and [Ru(
6-benzene)(
with a 1/14 complex/NaOH ratio [45]. From these preliminary
results, it can be concluded that the
6-p-cymene-ruthenium
complex, 1 and
6-benzene-ruthenium complex, 2 are more
h
6-p-cymene)(
-Cl)Cl]2 (37% maximum yield in 24 h)
m-Cl)Cl]2 (41% maximum yield in
h
m
4.4. Procedure for the preparation of transition metal complexes
h
h
6-p-cymene)Cl2], (1)
h
4.4.1. [Ru(Ph2PNHCH2-C4H3S)(
Compound 1 was prepared according to the published proce-
dure [23]. To a solution of [Ru( -Cl)Cl]2 (0.30 mg,
6-p-cymene)(
effective than those of the cod-Rh(I), 3 and Cp*-Ir(III), 4 complexes.
h
m
3. Conclusions
0.49 mmol) in CH2Cl2, a solution (thf, 30 mL) of [Ph2PNHCH2-
C4H3S], 1 (0.29 mg, 0.98 mmol) was added. The resulting reaction
mixture was allowed to proceed with stirring at room temperature
for 1 h. After this time, the solution was filtered and the solvent
evaporated under vacuum, the solid residue thus obtained was
washed with diethyl ether (3 ꢃ 15 mL) and then dried under
vacuum. Following recrystallization from diethyl ether/CH2Cl2,
a red crystalline powder was obtained. Yield 550 mg, 93.0%,
m.p. ¼ 180e182 ꢂC.
In summary, we have synthesized a series of selected transition-
metal (Ru(II), Rh(I), Ir(III)) complexes with the thiophene-2-(N-
diphenylphosphino)methylamine ligand. All the complexes were
characterized using multi nuclear NMR, IR and microanalysis and
also one representative structure was studied by single crystal X-
ray diffraction analysis. We have found that these complexes are
efficient homogeneous catalysts that can be readily employed in
transfer hydrogenation of ketones to alcohols with high conversion.
However, Ru(II)-aminophosphine complexes show higher catalytic
activity in the transfer hydrogenation reaction than the analogous
Rh(I) and Ir(III) complexes. Furthermore, the influence of arene ring
in the catalytic transfer hydrogenation of ketones was also inves-
tigated and it was found that their catalytic activities were very
similar.
4.4.2. Synthesis of [Ru(Ph2PNHCH2-C4H3S)(
Compound 2 was prepared according to the published proce-
dure [24]. mixture of [Ru( -Cl)Cl]2 (0.122 g,
6-benzene)(
h
6-benzene)Cl2], (2)
A
h
m
0.244 mmol) and [Ph2PNHCH2-C4H3S] (0.145 g, 0.488 mmol) in
20 mL of tetrahydrofuran was stirred at room temperature for 2 h.
The volume of the solvent was then reduced to 0.5 mL before
addition of diethyl ether (10 mL). The precipitated product was
filtered and dried in vacuo yielding 2 as a red microcrystalline
powder. Yield 245 mg, 92%, m.p. ¼ 186e188 ꢂC.
4. Experimental
4.1. General remarks
4.4.3. Synthesis of [Rh(Ph2PNHCH2-C4H3S)(cod)Cl], (3)
All reactions and manipulations were performed under argon
unless otherwise stated. Ph2PCl and thiophene-2-methylamine
were purchased from Fluka and used directly. Analytical grade
and deuterated solvents were purchased from Merck. Solvents
were dried using the appropriate reagents and distilled prior to use.
Compound 3 was prepared according to the published proce-
dure [24]. A mixture of [Rh(m-Cl)(cod)]2 (0.123 g, 0.244 mmol) and
[Ph2PNHCH2-C4H3S] (0.145 g, 0.488 mmol) in 20 mL of tetrahy-
drofuran was stirred at room temperature for 2 h. The volume of the
solvent was then reduced to 0.5 mL before addition of diethyl ether
(10 mL). The precipitated product was filtered and dried in vacuo
yielding 3 as a yellow microcrystalline solid. Yield 234 mg, 88%,
m.p. ¼ 214 ꢂC (dec.).
The starting materials [Ru(
benzene)( -Cl)Cl]2 [48], Rh(
Cl]2 [50] were prepared according to literature procedures. Infrared
h
6-p-cymene)(
m
-Cl)Cl]2 [46,47], [Ru(h6
5-C5Me5)(
-Cl)
-
m
m
-Cl)(cod)]2 [49], [Ir(
h
m

2588
M. Aydemir et al. / Journal of Organometallic Chemistry 696 (2011) 2584e2588
4.4.4. Synthesis of [Ir(Ph2PNHCH2-C4H3S)(h
5-C5Me5)Cl2], (4)
[8] C. Saluzzo, J. Breuzard, S. Pellet-Rostaing, M. Vallet, F.L. Guyader, M. Lemaire,
J. Organomet. Chem. 643-644 (2002) 98e104.
[9] N.W. Boaz, J.A. Ponasik, J. Large, E.S. Large, Tetrahedron: Asymmetry 16 (2005)
2063e2066.
Compound 4 was prepared according to the published proce-
dure [24]. mixture of [Ir( -Cl)Cl]2 (0.203 g,
A
h
5-C5Me5)(
m
[10] J.J. Reedijk, J. Chem. Soc. Chem. Commun. (1996) 801e806.
[11] P. Bhattacharyya, T.Q. Ly, A.M.Z. Slawin, J.D. Woollins, Polyhedron 20 (2001)
1803e1808.
[12] R.A.W. Johnstone, A.H. Wilby, I.N. Entwistle, Chem. Rev. 85 (1985) 129e170.
[13] H. Jiang, Q.D. Qiao, H. Gong, React. Kinet. Catal. Lett. 65 (1998) 1193e1197.
[14] R. Noyori, T. Ohkuma, Angew. Chem. Int. Ed. Engl. 40 (2001) 40e73.
[15] J. Canivet, G. Labat, H. Stockli-Evans, G. Süss-Fink, Eur. J. Inorg. Chem. (2005)
4493e4500.
0.244 mmol) and [Ph2PNHCH2-C4H3S] (0.145 g, 0.488 mmol) in
20 mL of tetrahydrofuran was stirred at room temperature for 2 h.
The volume of the solvent was then reduced to 0.5 mL before
addition of diethyl ether (10 mL). The precipitated product was
filtered and dried in vacuo yielding 4 as an orange microcrystalline
solid. Yield 312 mg, 92%, m.p. ¼ 204e206 ꢂC.
[16] P. Stepnicka, J. Ludvíc, J. Canivet, G. Süss-Fink, Inorganica Chim. Acta 359
(2006) 2369e2374.
4.5. X-ray diffraction structure analysis
[17] S.C. Stinson, Chem. Eng. News 77 (1999) 101e120.
[18] H.eU. Blaser, F. Spindler, M. Studer, Appl. Catal. A Gen. 221 (2001) 119e143.
[19] S. Gladiali, G. Mestroni, in: M. Beller, C. Bolm (Eds.), Transition Metal for
Organic Synthesis, 2, Wiley-VCH, Weinheim, 1998, pp. 97e119.
[20] J. Canivet, G. Süss-Fink, Green Chem. 9 (2007) 391e397.
[21] P. Govindaswamy, J. Canivet, B. Therrien, G. Süss-Fink, P. Stepnicka, J. Ludvik,
J. Organomet. Chem. 692 (2007) 3664e3675.
For the crystal structure determination, the single crystal of the
complex [Ru(Ph2PNHCH2eC4H3S)(h
6-benzene)Cl2], 2 was used for
data collection on a four-circle Rigaku R-AXIS RAPID-S diffractometer
(equipped with a two-dimensional area IP detector). The graphite-
[22] C. Botteghi, S. Paganelli, A. Schionato, M. Marchetti, Chirality
3 (1991)
monochromatized Mo Ka radiation (
l
¼ 0.71073 Å) and oscillation
355e369.
scans technique with Du ¼ 5ꢂ for one image were used for data
[23] M. Aydemir, A. Baysal, S. Özkar, L.T. Yıldırım, Polyhedron 30 (2011) 796e804.
[24] M. Aydemir, A. Baysal, Y. Turgut, Appl. Organomet. Chem. 25 (2011) 270e275.
[25] O.Y. Carreón, M.A. Leyva, G.J.M. Fernandez, A. Penicaud, Acta Crystallorg. C53
(1997) 301e302.
collection. The lattice parameters were determined by the least-
squares methods on the basis of all reflections with F2 > 2 (F2). H
s
atoms were positioned geometricallyand refined using a riding model.
Integration of the intensities, correction for Lorentz and polarization
effects and cell refinement was performed using CrystalClear software
[51]. The structures were solved by direct methods using SHELXS-97
[52] and refined by a full-matrix least-squares procedure using the
program SHELXL-97 [52]. The crystal data and structure refinement
details for compound 2 are given inTable 4. The final difference Fourier
maps showed no peaks of chemical significance.
[26] R.L. Cordiner, D. Corcoran, D.S. Yufit, A.E. Goeta, J.A.K. Howard, P.J. Low, Dalton
Trans. 18 (2003) 3541e3549.
[27] R.J. Mark Elsegood, M.B. Smith, N.M. Sanchez-Ballester, Acta Crystallorg. E62
(2006) m2838em2840.
[28] M.R.J. Elsegood, D.A. Tocher, Polyhedron 14 (1995) 3147e3156.
[29] B. Therrien, G. Süss-Fink, Inorg. Chim. Acta 357 (2004) 219e224.
[30] L. Vielle-Petit, B. Therrien, G. Süss-Fink, Eur. J. Inorg. Chem. 20 (2003)
3707e3711.
[31] R. Le Lagadec, L. Rubio, L. Alexandrova, R. Toscano, E.V. Ivanova, R. Meskys,
V. Laurinavicius, M. Pfeffer, A.D. Ryabov, J. Organomet. Chem. 689 (2004)
4820e4832.
[32] A.D. Ryabov, V.S. Kurova, V. Ekaterina, R. Ivanova, R. Le Lagadec,
L. Alexandrova, Anal. Chem. 77 (2005) 1132e1139.
Acknowledgments
[33] M. Aydemir, A. Baysal, J. Organomet. Chem. 695 (2010) 2506e2511.
[34] J.eX. Gao, P.eP. Xu, X.eD. Yi, C.eB. Yang, H. Zhang, S.eH. Cheng, H.eL. Wan,
K.eR. Tsai, T. Ikariya, J. Mol. Catal. A Chem. 147 (1999) 105e111.
[35] A.M. Maj, K.M. Pietrusiewicz, I. Suisse, F. Agbossou, A. Mortreux, J. Organomet.
Chem. 626 (2001) 157e160.
Partial support of this work by Turkish Academy of Sciences and
Dicle University (Project Number: DÜAPK 05-FF-27) is gratefully
acknowledged.
ꢀ
[36] M. Aydemir, F. Durap, A. Baysal, N. Meric, A. Buldag, B. Gümgüm, S. Özkar,
L.T. Yıldırım, J. Mol. Catal. A Chem. 326 (2010) 75e81.
[37] M. Aydemir, A. Baysal, S. Özkar, L.T. Yıldırım, Inorganica Chim. Acta 367 (2011)
166e172.
Appendix A. Supplementary material
[38] Y. Chen, S. Yekta, A.K. Yudin, Chem. Rev. 103 (2003) 3155e3211.
[39] T. Jerphagnon, J.eL. Renaud, C. Bruneau, Tetrahedron: Asymmetry 15 (2004)
2101e2111.
[40] M. Aydemir, A. Baysal, N. Meric, B. Gümgüm, J. Organomet. Chem. 694 (2009)
2488e2492.
CCDC-808703 contains the supplementary crystallographic data
for 2. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/conts/
retrieving.html or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK: Fax: (+44) 1223-
336-033, or e-mail: deposit@ccdc.cam.ac.uk.
[41] M. Aydemir, A. Baysal, Polyhedron 29 (2010) 1219e1224.
ꢀ
[42] M. Aydemir, N. Meric, F. Durap, A. Baysal, M. Togrul, J. Organomet. Chem. 695
(2010) 1392e1398.
ꢀ
[43] M. Aydemir, N. Meric, A. Baysal, C. Kayan, M. Togrul, B. Gümgüm, Appl.
Organomet. Chem. 24 (2010) 215e221.
[44] M. Aydemir, N. Meric, A. Baysal, B. Gümgüm, M. Togrul, Y. Turgut, Tetrahe-
References
ꢀ
dron: Asymmetry 21 (2010) 703e710.
[45] R. Tribo, S. Munoz, J. Pons, R. Yanez, A. Alvarez-Larena, J.F. Piniella, J. Ros,
J. Organomet. Chem. 690 (2005) 4072e4079.
[1] H.eJ. Chen, J.M. Barendt, R.C. Haltiwanger, T.G. Hill, A.D. Norman, Phosphorus
Sulfur Silicon Relat. Elem. 26 (1986) 155e162.
[46] M.A. Bennet, A.K. Smith, J. Chem. Soc. Dalton Trans. (1974) 233e241.
[47] M.A. Bennet, T.N. Huang, T.W. Matheson, A.K. Smith, Inorg. Synth. 7 (1982)
74e78.
[48] R.A. Zelonka, M.C. Baird, J. Organomet. Chem. 35 (1972) C43eC46.
[49] G. Giordano, R.H. Crabtree, Inorg. Synth. 28 (1990) 88e90.
[50] C. White, A. Yates, P.M. Maitliss, Inorg. Synth. 29 (1992) 228e230.
[51] Rigaku/MSC, Inc., 9009 new Trails Drive, The Woodlands, TX 77381.
[52] G.M. Sheldrick, SHELXS97 and SHELXL97. University of Göttingen, Germany,
1997.
[2] P. Bhattacharyya, J.D. Woollins, Polyhedron 14 (1995) 3367e3388.
[3] Y. Wang, X. Li, K. Ding, Tetrahedron Lett. 43 (2002) 159e161.
[4] S. Urgaonkar, J.G. Verkade, Adv. Synth. Catal. 346 (2004) 611e616.
[5] D.P. Catsoulocas, B.R. Steele, G.A. Herapoulos, M. Micha-Screttas, C.G. Screttas,
Tetrahedron Lett. 44 (2003) 4575e4578.
[6] J. Cheng, Y.H. Sun, F. Wang, M.J. Guo, J.H. Xu, Y. Pan, Z.G. Zhang, J. Org. Chem.
69 (2004) 5428e5430.
[7] M.L. Clarke, D.J. Cole-Hamilton, J.D. Woollins, J. Chem. Soc. Dalton Trans.
(2001) 2721e2723.