Synthesis of cyclopentadienyl ruthenium 4-pyridine and 2-pyrimidine thiolates and their bimetallic group VI metal carbonyls

Article abstract of DOI:10.1016/j.poly.2014.12.037

A simple one pot synthesis of CpRu(P-P)S-4-Py (Cp = η⁵-C₅H₅; P-P = dppm (1), dppe (2); Py = pyridine) and CpRu(P-P)S-2-Pym (P-P = dppm (3), dppe (4); Pym = pyrimidine) by the three component reaction of CpRu(PPh₃

Full text of DOI:10.1016/j.poly.2014.12.037

Polyhedron 89 (2015) 70–75
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Polyhedron
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Synthesis of cyclopentadienyl ruthenium 4-pyridine and 2-pyrimidine
thiolates and their bimetallic group VI metal carbonyls
a
a
b
b
Mohammad El-khateeb a, , Khaled Shawakfeh , Mazen Al-Btoosh , Helmar Görls , Wolfgang Weigand
⇑
a Chemistry Department, Jordan University of Science and Technology, Irbid 22110, Jordan
b Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldt Straße 8, 07743 Jena, Germany
a r t i c l e i n f o
a b s t r a c t
g
5-C5H5; P-P = dppm (1), dppe (2); Py = pyridine)
Article history:
A simple one pot synthesis of CpRu(P-P)S-4-Py (Cp =
Received 20 October 2014
Accepted 27 December 2014
Available online 10 January 2015
and CpRu(P-P)S-2-Pym (P-P = dppm (3), dppe (4); Pym = pyrimidine) by the three component reaction
of CpRu(PPh3)2Cl, thiolate anions and the diphosphine ligand has been accomplished. Complexes 1 and
2 reacted with M(CO)5THF at room temperature to give the new heterobimetallic complexes CpRu(P-
P)(
l
-4-SPy)(M(CO)5) [P-P = dppm (5), dppe (6); M = Cr (a), Mo (b), W (c)]. The corresponding reactions
2S,N)(M(CO)4) (P-P = dppm (7), dppe (8);
Keywords:
Ruthenium
Thiolates
Bimetallic complexes
X-ray structure
Group VI metal carbonyls
of 3 and 4 with M(CO)5THF produced CpRu(P-P)(
l
-2-SPym-
j
M = Cr (a), Mo (b), W(c)). These new complexes have been characterized by spectroscopic methods
(FT-IR, 1H and 31P NMR) and elemental analysis. The solid-state structures of CpRu(dppm)-4-SPy and
CpRu(dppe)-4-SPy have been determined by X-ray crystallography.
Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction
coordination sites, both of which might coordinate to the Ru center
[33]. The sulfur-coordinated heterocyclic thiolates CpRu(PPh3)2S-
Over the last few decades, great attention has been paid to orga-
noruthenium complexes containing thiolate ligands because of
their interesting structures, reactivity and applications [1–12].
They have found applications in chemical transformations of
organic molecules [6–9], in biological systems and as chemothera-
peutic agents used in cancer treatment [10–12].
het [het = furyl, thiophenyl, 2-imidazolyl, 1-methylimidazolyl,
5-methyl-1,3,5-thiadiazolyl, 5-methyl-4H-1,2,4-triazolyl] are
accessible from CpRu(PPh3)2Cl and heterocyclic thiolate anions
[29–32]. However, 2-pyridine thiolate and 2-pyrimidine thiolate
anions coordinated to the Ru through the N,S-atoms in a chelating
fashion, forming complexes of the formula CpRu(PPh3)(j
2S,N-S-
Several reports concerning ruthenium thiolato complexes with
phosphine ligands have been investigated [13–27]. The complexes
CpRu(PPh3)2SR have been made from CpRu(PPh3)2Cl and thiolate
anions [19,28]. Typically, these complexes undergo exchange reac-
tions with CO, NOBF4, P(OR)3 or bis(phosphine) (PP) ligands to give
the corresponding substituted products CpRu(CO)(PPh3)SR,
[CpRu(NO)(PPh3)SR]BF4, CpRu(P(OR)3)2SR or CpRu(PP)SR [15–
19,25,28]. The site of attack on the ruthenium thiolates in these
reactions is found to be the Ru center. On the other hand, the
reagents HBF4, R0Cl, R0Sphth (phth = phthalamide) attack the sulfur
atom of CpRu(PPh3)2SR to give respectively [CpRu(PPh3)(HSR)]+,
[CpRu(PPh3)(R0SR)]+ or [CpRu(PPh3)(R0SSR)]+ [26]. The complexes
CpRu(PPh3)2SR inserted CS2 into the Ru–S bond to give the trithio-
carbonato complexes CpRu(PPh3)(j2S,S-S2CSR) [28].
het) (het = 2-pyridine, 2-pyrimidine) [30]. These heterocyclic thiol-
ates reacted with CO gas and NOBF4 to give the mixed phosphine/
carbonyl complexes CpRu(PPh3)(CO)S-het or phosphine/nitrosyl
complex salts [CpRu(PPh3)(NO)S-het]+ [30]. In the presence of
bis(diphenylphosphino)alkane ligands (dppm or dppe) the reaction
of CpRu(PPh3)Cl and the heterocyclic thiolate anions produced the
phosphine-chelated
CpRu(
2P,P-dppe)S-het, respectively [30–32]. Herein, we demon-
strate a synthetic protocol for heterocyclic thiolato complexes of
ruthenium and their reactions as metallo-ligands with
complexes
CpRu(
j
2P,P-dppm)S-het
or
j
a
M(CO)5THF. Detailed characterization by spectroscopic, X-ray
structure determination and elemental analysis is provided.
2. Results and discussion
We have been interested in synthesizing ruthenium complexes
of heterocyclic thiolato ligands [29–32]. These ligands possess two
2.1. Synthesis of the thiolate complexes
⇑
Treatment of the ruthenium chloride complex CpRu(PPh3)2Cl
with 4-pyridine thiolate or 2-pyrimidine thiolate anions in the
Corresponding author.
E-mail address: kateeb@just.edu.jo (M. El-khateeb).
http://dx.doi.org/10.1016/j.poly.2014.12.037
0277-5387/Ó 2015 Elsevier Ltd. All rights reserved.

M. El-khateeb et al. / Polyhedron 89 (2015) 70–75
71
presence of bis(diphenylphosphino)methane or bis(diphenylphos-
phino)ethane ligands resulted in the formation of CpRu(PP)S-4-Py
or CpRu(PP)S-2-Pym according to Scheme 1.
The thiolato complexes 1–4 are stable solids and air sensitive in
solution. The structures of these complexes were fully character-
ized by spectral and elemental analysis data. The solid state struc-
tures of 1 and 2 were determined by single crystal X-ray analysis.
The 1H NMR spectra of complexes 1–4 showed a singlet peak in
the range 4.79–5.00 ppm for the Cp protons. These values are
within the same range reported for thiolato and sulfonato com-
plexes [18]. The methylene protons of the dppm or dppe ligands
of 1–4 appeared as two multiplets due to coupling to each other
and to the P-atoms [30]. The protons of the heterocyclic groups
resonate within the expected ranges and with the expected multi-
plicities [28–32]. The 31P NMR spectra of complexes 1–4 were
determined and showed a singlet peak for the identical P-atoms.
This singlet is found at 17.83 and 17.26 ppm for 1 and 3, respec-
tively and at 77.74 and 79.63 ppm for 2 and 4, in accordance with
the reported values of similar systems [18,30].
Fig. 1. Molecular structure and numbering scheme of 1. The ellipsoids represent a
probability of 40%.
2.2. Crystal structures of 1 and 2
The structures of complexes 1 and 2 were determined by X-ray
crystallography and are shown in Figs. 1 and 2 respectively. Table 1
shows selected bond lengths (Å) and angles (°) of these complexes.
Cyclopentadienyl ruthenium(II) complexes commonly adopt a
piano stool structure with three legs. The Ru–C(Cp) bond distances
are in the range 2.200(3)–2.257(3) Å for 1 and 2.205(3)–2.259(3) Å
for 2, similar to those reported for similar systems [18,24,34]. The
Ru–S bond distance of 1 (2.3889(7) Å) is a bit shorter than that of 2
(2.3907(7) Å) and the corresponding distances in [CpRu(PPh3)
(NO)(j1S-HSpy)]BF4 and CpRu(PPh3)(CO)(j1S-Spy) [30]. The Ru–P
bond distances of 1 (2.2659(7), 2.2984(7) Å) and 2 (2.2909(7),
2.2616(8) Å) are in the same range observed for the thiocarbonato
complexes CpRu(PP)SCO2R [35]. The sulfur atom is sp3-hybridized,
as indicated by the Ru–S–C1 angle (1: 111.70(10)°, 2: 112.25(10)°).
The coordination around the ruthenium center is distorted octahe-
dral, as indicated by the P1–Ru–P2, P1–Ru–S and P2–Ru–S bond
angles. A noticeable difference between the P–Ru–P bond angles
observed for 1 and 2 is observed and this may be attributed to
the four membered ring obtained by the dppm ligand versus the
five membered one of the dppe ligand. Molecule 2 contains an eth-
anol molecule bound to the N-atom of the pyridine ring of the thio-
late group via a hydrogen bonding interaction with an N. . .H
distance of 2.00 Å and N–H–O bond angle of 163.5°.
Fig. 2. Molecular structure and numbering scheme of 2. The ellipsoids represent a
probability of 40%.
2.3. Synthesis of the bimetallic complexes
The 4-pyridine thiolato complexes 1 and 2 react at room tem-
perature with M(CO)5THF (M = Cr, Mo, W) in THF to give bimetallic
complexes, as shown in Eq. (1). On the other hand, the correspond-
ing pyrimidine thiolato complexes 3 and 4 react with the metal
pentacarbonyl intermediates to give the bridging N,S-chelated
bimetallic complexes shown in Eq. (2).
S-
N
Ru
N
P
S
P
P-P = dppm (1), dppe (2)
P
P
+
Ru
Ph3P
Cl
S-
PPh3
N
N
Ru
P
N
N
P
S
P-P = dppm (3), dppe (4)
Scheme 1.

72
M. El-khateeb et al. / Polyhedron 89 (2015) 70–75
Table 1
Selected bond lengths (Å) and angles (°) for complexes 1 and 2.
1
2ꢁEtOH
Ru–C6
Ru–C10
Ru–C7
Ru–C9
Ru–C8
Ru–P1
Ru–P2
Ru–S
2.200(3)
2.202(3)
2.242(3)
2.241(3)
2.257(3)
2.2659(7)
2.2984(7)
2.3889(7)
1.751(3)
Ru–C6
Ru–C10
Ru–C7
Ru–C9
Ru–C8
Ru–P1
Ru–P2
Ru–S
2.259(3)
2.235(3)
2.257(3)
2.205(3)
2.206(3)
2.2909(7)
2.2616(8)
2.3907(7)
1.745(3)
S–C1
S–C1
P1–Ru–S
P2–Ru–S
P1–Ru–P2
Ru–S–C1
87.89(3)
92.10(3)
71.43(3)
111.70(10)
P1–Ru–S
P2–Ru–S
P1–Ru–P2
Ru–S–C1
93.26(3)
83.42(3)
83.90(3)
112.25(10)
OC
CO
CO
Ru
Ru
+ M(CO)5THF
N
P
S
M
CO
P
S
N
P
P
OC
P-P = dppm (1), dppe (2)
P-P = dppm (5), dppe (6)
a
b
c
ð1Þ
M = Cr ( ), Mo ( ), W ( )
N
N
Fig. 4. IR spectrum of CpRu(dppm)(l-2-SPym-j
2-S,N)(Cr(CO)4), 8a.
Ru
Ru
+
M(CO)5THF
P
P
S
S
P
P
N
N
OC
OC
M
characterized by FT-IR, 1H and 31P NMR spectroscopic techniques,
as well as by elemental analysis. In the IR spectra of 5 and 6
(Fig. 3 as a representative example), three typical absorption peaks
were observed in the ranges 2062–2069, 1923–1932 and 1888–
1894 cmꢀ1 as expected for pentacarbonyl complexes having a C4V
local symmetry [36–38]. On the other hand, the corresponding
spectra of 7 and 8 display a 4-band-pattern observed for the C2V
local symmetry [38]. This clearly indicates the presence of a
M(CO)4 moiety, rather than the M(CO)5, as shown in the above
equations. These bands are found within the ranges 2000–2009,
1876–1894, 1860–1871 and 1830–1835 cmꢀ1, and are similar to
those reported for complexes containing the M(CO)4 moiety [36–
38]. Fig. 4 shows a representative IR spectrum of CpRu(dppm)
CO
CO
P-P = dppm (3), dppe (4)
P-P = dppm (7), dppe (8)
M = Cr (a), Mo (b), W (c)
ð2Þ
The bimetallic complexes 5a–8c are orange, air stable solids and
are air sensitive in solution. They are soluble in common organic
polar solvents and insoluble in hydrocarbons. They have been
(l
-2-SPym-
j
2-S,N)(Cr(CO)4), 8a.
The 1H NMR spectra for complexes 5 and 6 show singlet peaks
in the ranges 4.99–5.00 and 4.92–4.94 ppm, respectively, for the
five equivalent Cp-protons. These ranges are at higher chemical
shift values than those of the parent complexes 1 and 2. This result
indicates that the electron density around the ruthenium is
reduced by complexation with the M(CO)5 moiety to the N-atom
of the pyridine ligand. The corresponding peaks of complexes 7
and 8 are shown in the ranges 4.80–4.84 and 4.83–4.88 ppm,
respectively, which are high field shifted compared to those of 3
and 4. The CH2 groups of the phosphine ligands in 5–8 complexes
show their presence in the spectra as two multiplets for each com-
pound due to the two non-equivalent hydrogen types. The protons
of the pyrimidine or pyridine groups appear in the expected posi-
tions with the expected multiplicities.
The 31P NMR spectra of the bis(diphenylphosphino)methane
complexes
5 and 7 display singlet peaks in the ranges
17.70–18.62 and 13.08–16.60 ppm, respectively for the equivalent
P-atoms. The corresponding spectra of the bis(diphenylphos-
phino)ethane complexes show also
a singlet in the ranges
82.60–83.55 and 85.90–87.73 ppm, respectively. Although these
later values are clearly at higher chemical shifts compared to those
of the parent complexes (2 and 4), those of the dppm-complexes (5
and 7) are either similar or at lower ppm values than those of the
Fig. 3. IR spectrum of CpRu(dppm)(l-4-SPy)(Mo(CO)5), 5b.

M. El-khateeb et al. / Polyhedron 89 (2015) 70–75
73
parent molecules (1 and 3). These results indicate lower electron
density around the P atom of the dppe-dimeric complexes, which
is not the case in the dppm analogues.
3.2.2. General procedure for the preparation of CpRu(P-P)(
(M(CO)5), [M = Cr, Mo, W]
l-4-SPy)-
In a 250 mL two neck flask, CpRu(P-P)-4-SPy (0.30 mmol) was
added to a 200 mL M(CO)5THF solution and the resulting mixture
was stirred overnight. The volume of the mixture was concentrated
under vacuum to about 5 mL and then 40–50 mL of hexane was
added. Cooling this solution overnight gave the product as orange
crystals, which were separated and washed several times with
hexane.
3. Experimental part
3.1. General
All reactions and manipulations were carried out under a nitro-
gen atmosphere using Schlenk line techniques. Hexane and THF
were dried over Na/benzophenone and freshly distilled prior to
use. Ethanol was dried by sodium and freshly distilled prior
to use. 2-Mercaptopyrimidine, 4-mercaptopyridine, ruthe-
nium(III)chloride hydrate, 1,2-bis(diphenylphosphino)ethane, 1,1-
bis(diphenylphosphino)methane and M(CO)6 [M = Cr, Mo, W] were
used as received from commercial sources. CpRu(PPh3)2Cl was pre-
pared as described in the literature [39].
CpRu(dppm)(
l
-4-SPy)(Cr(CO)5) (5a): Yield 79%. M.p.: 204–
206 °C. FT-IR (THF, cmꢀ1):
m
(CO) = 2062 w, 1926 vs 1892 sh. 1H
NMR ((CD3)2CO) d: 4.77 (m, 1H, PCH2), 4.99 (s, 5H, C5H5), 5.11
(m, 1H, PCH2), 6.80 (d, 2H, C5H4N, JHH = 4.00 Hz), 7.30 (m, 12H,
PPh2), 7.49 (m, 8H, PPh2), 7.69 (m, 2H, C5H4N). 31P NMR ((CD3)2CO)
d: 17.91. Anal. Calc. for C40H31CrNO5P2RuS: C, 56.34; H, 3.66; N,
1.64; S, 3.76. Found: C, 55.60; H, 3.55; N, 1.67; S, 3.80%.
CpRu(dppm)(
l
-4-SPy)(Mo(CO)5) (5b): Yield 66%. M.p.: 229–
231 °C. FT-IR (THF, cmꢀ1):
m
(CO) = 2068 w, 1932 vs 1891 m. 1H
The FT-IR spectra were recorded on a JASCO FT-IR spectropho-
tometer employing a 0.1 mm NaCl solution cell. 1H and 31P NMR
spectra were recorded on a Bruker AVANCE 400 MHz spectrome-
ter. Chemical shifts were recorded in ppm downfield of TMS with
NMR ((CD3)2CO) d: 4.77 (m, 1H, PCH2), 5.00 (s, 5H, C5H5), 5.10
(m, 1H, PCH2), 6.84 (d, 2H, C5H4N, JHH = 6.00 Hz), 7.31 (m, 12H,
PPh2), 7.50 (m, 8H, PPh2), 7.54 (d, 2H, C5H4N). 31P NMR ((CD3)2CO)
d: 18.62. Anal. Calc. for C40H31MoNO5P2RuS: C, 53.58; H, 3.48; N,
1.56; S, 3.58. Found: C, 53.05; H, 3.52; N, 1.58; S, 3.68%.
the solvent as
a
reference signal ((CD3)2CO: 1H NMR,
d = 2.05 ppm). Melting points were recorded by a Melting Point
Apparatus SMP3, Stuart scientific. Elemental analyses were per-
formed by a EuroEA Elemental Analyzer.
CpRu(dppm)(
l
-4-SPy)(W(CO)5) (5c): Yield 42%. M.p.: 354–
355 °C. FT-IR (THF, cmꢀ1):
m
(CO) = 2069 w, 1926 vs 1894 sh. 1H
NMR ((CD3)2CO) d: 4.76 (m, 1H, PCH2), 5.00 (s, 5H, C5H5), 5.11
(m, 1H, PCH2), 6.83 (d, 2H, C5H4N, JHH = 6.80 Hz), 7.24 (m, 8H,
PPh2), 7.47 (m, 12H, PPh2), 7.55 (m, 2H, C5H4N). 31P
NMR ((CD3)2CO) d: 17.70. Anal. Calc. for C40H31NO5P2RuSW: C,
48.79; H, 3.17; N, 1.42; S, 3.26. Found: C, 48.60; H, 3.42; N, 1.66;
S, 3.18%.
3.2. Preparation of the complexes
3.2.1. General procedure for the preparation of CpRu(P-P)-4-Spy and
CpRu(P-P)-2-Spym
The heterocyclic thiol (1.00 mmol) and sodium metal
(1.00 mmol, 0.023 g) were dissolved in absolute ethanol (25 mL).
The CpRu(PPh3)2Cl complex (0.68 mmol, 0.50 g) and the bis(diph-
osphino)alkane ligand (0.82 mmol) were dissolved in THF and
added to the EtOH solution, and the resulting mixture was refluxed
for 4 h. The volatiles were removed under vacuum and the residue
was extracted with 10 mL of toluene. Addition of 40–50 mL hexane
followed by standing gave the product as an orange precipitate,
which was collected by removing the mother liquor by syringe.
The product was washed several times with cooled hexane and
recrystallized from THF/hexane.
CpRu(dppe)(
l
-4-SPy)(Cr(CO)5) (6a): Yield 78%. M.p.: 194–196 °C.
FT-IR (THF, cmꢀ1):
m
(CO) = 2063 w, 1928 vs 1891 m. 1H NMR
((CD3)2CO) d: 2.25 (m, 2H, PCH2), 2.79 (m, 2H, PCH2), 4.92 (s, 5H,
C5H5), 6.60 (d, 2H, C5H4N, JHH = 5.60 Hz), 7.27 (m, 6H, PPh2), 7.40
(m, 12H, PPh2), 7.64 (m, 4H, C5H4N + PPh2). 31P NMR ((CD3)2CO)
d: 82.60. Anal. Calc. for C41H33CrNO5P2RuS: C, 56.80; H, 3.84; N,
1.62; S, 3.70. Found: C, 55.62; H, 3.93; N, 1.78; S, 3.80%.
CpRu(dppe)(
l
-4-SPy)(Mo(CO)5) (6b): Yield 89%. M.p.: 140–
142 °C. FT-IR (THF, cmꢀ1):
m
(CO) = 2068 w, 1931 vs 1891 m. 1H
NMR ((CD3)2CO) d: 2.25 (m, 2H, PCH2), 2.81 (m, 2H, PCH2), 4.92
(s, 5H, C5H5), 6.61 (d, 2H, C5H4N, JHH = 6.80 Hz), 7.27 (m, 8H,
PPh2), 7.40 (m, 12H, PPh2), 7.64 (m, 2H, C5H4N). 31P NMR
((CD3)2CO) d: 83.55. Anal. Calc. for C41H33MoNO5P2RuS: C, 54.07;
H, 3.65; N, 1.54; S, 3.52. Found: C, 53.99; H, 3.89; N, 1.49; S, 3.40%.
CpRu(dppm)-4-SPy (1): Yield 83%. M.p.: 254–256 °C. 1H NMR
((CD3)2CO) d: 4.78 (m, 1H, PCH2), 4.95 (s, 5H, C5H5), 5.10 (m, 1H,
PCH2), 6.79 (d, 2H, C5H4N), 7.21 (m, 8H, PPh2), 7.46 (m, 12H,
PPh2), 7.56 (d, 2H, C5H4N, JHH = 6.00 Hz). 31P NMR ((CD3)2CO) d:
17.83. Anal. Calc. for C35H31NP2RuS: C, 63.62; H, 4.73; N, 2.12; S,
4.86. Found: C, 63.87; H, 4.55; N, 2.18 S, 4.85%.
CpRu(dppe)(
l
-4-SPy)(W(CO)5) (6c): Yield 73%. M.p.: 279–280 °C.
FT-IR (THF, cmꢀ1):
m
(CO) = 2066 w, 1923 vs 1888 m. 1H NMR
((CD3)2CO) d: 2.28 (m, 2H, PCH2), 2.80 (m, 2H, PCH2), 4.94 (s, 5H,
C5H5), 6.64 (d, 2H, C5H4N, JHH = 5.80 Hz), 7.28 (m, 8H, PPh2), 7.40
(m, 12H, PPh2), 7.65 (m, 2H, C5H4N). 31P NMR ((CD3)2CO) d:
83.50. Anal. Calc. for C41H33NO5P2RuSW: C, 49.31; H, 3.33; N,
1.40; S, 3.21. Found: C, 49.60; H, 3.09; N, 1.60; S, 2.98%.
CpRu(dppe)-4-SPy (2): Yield 84%. M.p.: 209–210 °C. 1H NMR
((CD3)2CO) d: 2.25 (m, 2H, PCH2), 3.54 (m, 2H, PCH2), 4.79 (s, 5H,
C5H5), 6.54 (d, 2H, C5H4N, JHH = 4.80 Hz), 7.22 (m, 8H, PPh2), 7.34
(m, 12H, PPh2), 7.64 (m, 2H, C5H4N). 31P NMR ((CD3)2CO) d:
77.74. Anal. Calc. for C36H33NP2RuS: C, 63.32; H, 4.45; N, 1.94; S,
4.45. Found: C, 62.83; H, 4.40; N, 2.10; S, 4.23%.
3.2.3. General procedure for the preparation of CpRu(P-P)(
2-S,N)(M(CO)4), [M = Cr, Mo, W]
In a 250 mL two neck flask, CpRu(P-P)-2-SPym (0.30 mmol) was
l-2-SPym-
CpRu(dppm)-2-SPym (3): Yield 84%. M.p.: 260–261 °C. 1H NMR
((CD3)2CO) d: 4.63 (m, 1H, PCH2), 5.00 (s, 5H, C5H5), 5.25 (m, 1H,
PCH2), 6.40 (m, 1H, C4H3N2), 7.19 (m, 8H, PPh2), 7.60 (m, 12H,
PPh2), 7.80 (d, 2H, C4H3N2). 31P NMR ((CD3)2CO) d: 17.26. Anal. Calc.
for C34H30N2P2RuS: C, 61.71; H, 4.57; N, 4.23; S, 4.85. Found: C,
60.88; H, 4.52; N, 4.35; S, 4.60%.
CpRu(dppe)-2-Spym (4): Known compound [30]. Yield 94%. M.p.:
178–180 °C. 1H NMR ((CD3)2CO) d: 1.23 (m, 2H, PCH2), 2.85 (m, 2H,
PCH2), 4.87 (s, 5H, C5H5), 6.87 (d, 1H, C4N2H3), 7.35 (m, 20H, PPh2),
7.78 (t, 1H, C4N2H3), 7.58 (d, 1H, C4N2H3). 31P NMR ((CD3)2CO) d:
79.63. Anal. Calc. for C35H32N2P2RuS: C, 62.21; H, 4.77; N, 4.14; S,
4.74. Found: C, 61.90; H, 4.46; N, 4.65; S, 5.15%.
j
added to a 200 mL M(CO)5THF solution and the resulting mixture
was stirred overnight. The volume of the mixture was concentrated
under vacuum to about 5 mL and then 40–50 mL of hexane was
added. Cooling this solution overnight gave the product as orange
crystals, which were separated and washed several times with
hexane.
CpRu(dppm)(l
-2-SPym-j2-S,N)(Cr(CO)4) (7a): Yield 79%. M.p.:
167–169 °C. FT-IR (THF, cmꢀ1):
m(CO) = 2000 w, 1885 vs 1867 sh,
1831 s. 1H NMR ((CD3)2CO) d: 4.84 (s, 5H, C5H5), 4.95 (m, 2H,
PCH2), 6.46 (s, 1H, C4H3N2), 7.26 (m, 8H, PPh2), 7.58 (m, 12H,

74
M. El-khateeb et al. / Polyhedron 89 (2015) 70–75
PPh2), 7.73 (m, 2H, C4H3N2). 31P NMR ((CD3)2CO) d: 16.66. Anal.
Calc. for C38H30CrN2O4P2RuS: C; 55.27; H, 3.66; N, 3.39; S, 3.88.
Found: C, 55.90; H, 3.78; N, 3.49; S, 3.63%.
group P21/c, a = 12.3369(4), b = 16.6008(6), c = 16.8852(5) Å,
b = 106.988(2)°, V = 3307.24(19) Å3, T = ꢀ90 °C, Z = 4, qcalcd.
=
1.448 g cmꢀ3
,
l(Mo
Ka
) = 6.66 cmꢀ1
,
multi-scan, transmin:
CpRu(dppm)(
l
-2-SPym-
j
2-S,N)(Mo(CO)4) (7b): Yield 67%. M.p.:
(CO) = 2009 w, 1890 vs 1871 sh,
0.6934, transmax: 0.7546, F(000) = 1488, 22661 reflections in h
(ꢀ15/15), (ꢀ21/21), (ꢀ21/20), measured in the range
2.12° 6 6 27.47°, completeness max = 99.8%, 7559 indepen-
dent reflections, Rint = 0.0683, 5133 reflections with Fo > 4 (Fo),
399 parameters,
restraints, R1obs = 0.0392, wR2obs = 0.0775,
191–193 °C. FT-IR (THF, cmꢀ1):
m
k
l
1835 m. 1H NMR ((CD3)2CO) d: 4.84 (s, 5H, C5H5), 5.66 (m, 2H,
PCH2), 6.58 (m, 1H, C4H3N2), 7.26 (m, 8H, PPh2), 7.37 (m, 12H,
PPh2), 8.02 (m, 2H, C4H3N2). 31P NMR ((CD3)2CO) d: 13.69. Anal.
Calc. for C38H30MoN2O4P2RuS: C, 52.48; H, 3.48; N, 3.22; S, 3.91.
Found: C, 51.88; H, 3.55; N, 3.31; S, 3.98%.
H
H
r
0
R1all = 0.0802, wR2all = 0.0898, Goodness-of-fit = 0.949, largest differ-
ence peak and hole: 0.619/ꢀ0.553 e Åꢀ3
.
CpRu(dppm)(
l
-2-SPym-j2-S,N)(W(CO)4) (7c): Yield 38%. M.p.:
(CO) = 2000 w, 1876 vs 1864 sh,
223–225 °C. FT-IR (THF, cmꢀ1):
m
4. Conclusion
1830 m. 1H NMR ((CD3)2CO) d: 4.80 (s, 5H, C5H5), 5.58 (m, 2H,
PCH2), 6.62 (s, 1H, C4H3N2), 7.27 (m, 8H, PPh2), 7.50 (m, 12H,
PPh2), 8.15 (m, 2H, C4H3N2). 31P NMR ((CD3)2CO) d: 13.08. Anal.
Calc. for C38H30N2O4P2RuSW: C, 47.66; H, 3.16; N, 2.93; S, 3.35.
Found: C, 46.87; H, 3.07; N, 3.09; S, 3.42%.
The work presented in this paper demonstrates the synthesis of
heterocyclic thiolato complexes of ruthenium. Bimetallic com-
plexes containing Ru(II) in addition to group VI metals in the zero
oxidation state were also synthesized. The 4-pyridine thiolato
complexes coordinated to the M(CO)5 moiety in a monodentate
fashion, while those of the 2-pyrimidine complexes coordinated
in a chelated SN-fashion.
CpRu(dppe)(
l
-2-SPym-j2-S,N)(Cr(CO)4) (8a): Yield 82%. M.p.:
(CO) = 2002 w, 1888 vs 1866 sh,
132–133 °C. FT-IR (THF, cmꢀ1):
m
1832 s. 1H NMR ((CD3)2CO) d: 3.00 (m, 2H, PCH2), 3.16 (m, 2H,
PCH2), 4.84 (s, 5H, C5H5), 6.56 (m, 1H, C4H3N2), 7.23 (m, 8H,
PPh2), 7.34 (m, 12H, PPh2), 7.88 (m, 2H, C4H3N2). 31P NMR ((CD3)2-
CO) d: 85.90. Anal. Calc. for C39H32CrN2O4P2RuS: C, 55.78; H, 3.84;
N, 3.34; S, 3.82. Found: C, 55.71; H, 3.75; N, 3.28; S, 3.70%.
Acknowledgements
The authors acknowledge the Deanship of Research, Jordan Uni-
versity of Science and Technology – Jordan for financial support,
Grant No. (166/2008).
CpRu(dppe)(
l
-2-SPym-
j
2-S,N)(Mo(CO)4) (8b): Yield 90%. M.p.:
(CO) = 2009 w, 1894 vs 1870 sh,
125–128 °C. FT-IR (THF, cmꢀ1):
m
1835 s. 1H NMR ((CD3)2CO) d: 2.90 (m, 2H, PCH2), 3.14 (m, 2H,
PCH2), 4.83 (s, 5H, C5H5), 6.65 (t, 1H, C4H3N2), 7.19 (m, 8H, PPh2),
7.32 (m, 12H, PPh2), 7.84 (m, 2H, C4H3N2). 31P NMR ((CD3)2CO) d:
87.34. Anal. Calc. for C39H32MoN2O4P2RuS: C, 53.01; H, 3.65; N,
3.17; S, 3.63. Found: C, 52.34; H, 3.71; N, 3.15; S, 3.63%.
Appendix A. Supplementary data
CCDC 1028083 and 1028084 contain the supplementary crys-
tallographic data for complexes 1 and 2, respectively. These data
can be obtained free of charge via http://www.ccdc.cam.ac.uk/con-
ts/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.
CpRu(dppe)(
l
-2-SPym-j2-S,N)(W(CO)4) (8c): Yield 86%. M.p.:
(CO) = 2002 w, 1880 vs 1860 sh,
153–155 °C. FT-IR (THF, cmꢀ1):
m
1831 s. 1H NMR ((CD3)2CO) d: 2.99 (m, 2H, PCH2), 3.17 (m, 2H,
PCH2), 4.83 (s, 5H, C5H5), 6.71 (m, 1H, C4H3N2), 7.23 (m, 8H,
PPh2), 7.32 (m, 12H, PPh2), 8.14 (m, 2H, C4H3N2). 31P NMR
((CD3)2CO) d: 87.73. Anal. Calc. for C39H32N2O4P2RuSW: C, 48.21;
H, 3.32; N, 2.88; S, 3.30. Found: C, 47.94; H, 3.41; N, 2.99; S, 3.44%.
References
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3.3. X-ray crystal structure analysis
Diffraction quality single crystals of 1 and 2 were obtained from
a THF/hexane mixture at low temperature. The intensity data were
collected on a Nonius KappaCCD diffractometer, using graphite-
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Crystal data for 1: C35H31NP2RuS, Mr = 660.68 g molꢀ1, red-
brown prism, size 0.045 ꢂ 0.035 ꢂ 0.032 mm3, triclinic, space
ꢀ
group P1, a = 9.6077(3), b = 11.6099(4), c = 14.5177(5) Å,
a =
84.635(2), b = 89.814(2),
c
= 67.645(2)°, V = 1490.19(9) Å3, T =
ꢀ90 °C, Z = 2,
q
calcd. = 1.472 g cmꢀ3
,
l
(Mo K
a
) = 7.29 cmꢀ1, multi-
scan, transmin: 0.6573, transmax: 0.7456, F(000) = 676, 10517
reflections in h (ꢀ12/12), k (ꢀ13/15), l (ꢀ18/18), measured in the
range 2.29° 6
H 6 27.50°, completeness Hmax = 99.1%, 6789
independent reflections, Rint = 0.0296, 5543 reflections with Fo >
4
r
(Fo), 361 parameters, 0 restraints, R1obs = 0.0395, wR2obs = 0.0951,
R
1all = 0.0559, wR2all = 0.1036, Goodness-of-fit = 1.039, largest differ-
ence peak and hole: 0.595/ꢀ0.835 e Åꢀ3
.
Crystal data for 2: C36H33NP2RuS.C2H5OH, Mr = 720.77 g molꢀ1
,
yellow prism, size 0.042 ꢂ 0.034 ꢂ 0.032 mm3, monoclinic, space

M. El-khateeb et al. / Polyhedron 89 (2015) 70–75
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