Monomeric and dimeric ruthenium thiooxalate complexes: Structures of CpRu(PPh3)2SCOCO2Me and CpRu(dppe)SCOCO2Et

Article abstract of DOI:10.1016/j.jorganchem.2006.05.018

The hydrosulfido complexes CpRu(L)(L′)SH react with one equivalent of O-alkyl oxalyl chlorides (ROCOCOCl) to form the corresponding O-alkylthiooxalate complexes CpRu(L)(L′)SCOCO₂R (L = L′ = PPh₃ (1), frac(1, 2) dppe (2); L = PPh₃, L′ = CO (3); R = Me (a), Et (b)). The reactions of the hydrosulfido complexes with half equivalent of oxalyl chloride produce the bimetallic complexes [CpRu(L)(L′)SCO]₂ (L = L′ = PPh₃ (4), frac(1, 2) dppe (5); L = PPh₃, L′ = CO (6)). The crystal structures of CpRu(PPh₃)₂SCOCO₂Me (1a) and CpRu(dppe)SCOCO₂Et (2b) are reported.

Full text of DOI:10.1016/j.jorganchem.2006.05.018

Journal of Organometallic Chemistry 691 (2006) 3743–3748
www.elsevier.com/locate/jorganchem
Monomeric and dimeric ruthenium thiooxalate complexes: Structures
of CpRu(PPh3)2SCOCO2Me and CpRu(dppe)SCOCO2Et
a,
a
b
b
Mohammad El-khateeb *, Khaled Shawakfeh , Tobias Ruffer , Heinrich Lang
¨
a
Chemistry Department, Jordan University of Science and Technology, Irbid 22110, Jordan
Technische Universita¨t Chemnitz, Institut fu¨r Chemie, Lehrstuhl Anorganische Chemie, Strasse der Nationen 2, Chemnitz 09111, Germany
b
Received 29 March 2006; received in revised form 11 May 2006; accepted 11 May 2006
Available online 20 May 2006
Abstract
The hydrosulfido complexes CpRu(L)(L0)SH react with one equivalent of O-alkyl oxalyl chlorides (ROCOCOCl) to form the corre-
1
sponding O-alkylthiooxalate complexes CpRu(L)(L0)SCOCO2R (L = L0 = PPh3 (1), dppe (2); L = PPh3, L0 = CO (3); R = Me (a), Et
2
(b)). The reactions of the hydrosulfido complexes with half equivalent of oxalyl chloride produce the bimetallic complexes
1
[CpRu(L)(L0)SCO]2 (L = L0 = PPh3 (4), dppe (5); L = PPh3, L0 = CO (6)). The crystal structures of CpRu(PPh3)2SCOCO2Me (1a)
2
and CpRu(dppe)SCOCO2Et (2b) are reported.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; O-alkylthiooxalate; Sulfur; Triphenylphosphine; Diphenylphosphinoethane; Carbonyl; Complexes; Solid-state structure
1. Introduction
one was prepared by a one-pot reaction of CpRu(PPh3)2Cl,
dppe and NaSH, while the second one is accessible from
CpRu(dppm)Cl and NaSH [11].
The coordination chemistry and reactivity of hydrosulf-
ido metal complexes, [M]–SH, are of current interest
because of their structural diversity, relevant to metalloen-
zymes and industrial processes such as hydrodesulfuriza-
tion and Claus chemistry [1–4]. The reaction of these
hydrosulfido complexes with sulfur dioxide (to give [M]-
SS(O)OH) has been proposed as a key step in the Claus
process [5,6] and also in the hydrogenation of sulfur diox-
ide [7,8].
The bis(triphenylphosphine) hydrosulfido ruthenium
complex CpRu(PPh3)2SH is prepared by a metathesis reac-
tion of the corresponding ruthenium chloride with NaSH
[9,10]. Treatment of this hydrosulfido complex with CO
gas at room temperature produces the mixed carbonyl-
phosphine complex CpRu(PPh3)(CO)SH in good isolated
yield [9]. The chelate complexes CpRu(dppe)SH and
CpRu(dppm)SH have been also reported of which the first
The ruthenium hydrosulfido complexes CpRu(L)(L0)SH
are quite reactive toward a variety of electrophiles [10–12].
The reaction of CpRu(PPh3)2SH with carbon disulfide is
reported to produce the bimetallic complex CpRu(PPh3)-
(j2S,S-S2C)SRu(PPh3)2Cp via insertion of CS2 into the
Ru–S bond to give CpRu(PPh3)(j2S,S-S2CSH) followed
by its reaction with another equivalent of CpRu(PPh3)2SH
[10]. On the other hand, complexes CpRu(L)(L0)SH
1
1
(L = L0 = PPh3, dppm; dppe) give with acid chlorides at
2 2
low temperature the corresponding thiocarboxylate com-
plexes CpRu(L)(L0)SCOCH2-4-C6H4X (X = H, Me,
OMe, Cl) [12]. The mixed carbonyl-phosphine analogs
CpRu(PPh3)(CO)SCOCH2-4-C6H4X have been prepared
by the reaction of CpRu(PPh3)2SCOCH2-4-C6H4X with
CO [12]. The reaction of the chelate hydrosulfido com-
plexes CpRu(dppa)SH (dppa = dppm, dppe) with various
sulfonyl chlorides afforded the expected thiosulfonato spe-
cies CpRu(L)(L0)SSO2R [13]. Recently, the reaction of
these hydrosulfido complexes with chloroformates
*
Corresponding author. Tel.: +962 2 7201000; fax: +962 2 7095014.
E-mail address: kateeb@just.edu.jo (M. El-khateeb).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.05.018

3744
M. El-khateeb et al. / Journal of Organometallic Chemistry 691 (2006) 3743–3748
(ROCOCl) were found to produce the appropriate thiocar-
bonate complexes CpRu(L)(L0)SCO2R (L = L0 = PPh3,
12dppe; L = PPh3, L0 = CO; R = alkyl, aryl) [14].
As an extension to our work in this area, we here
describe the synthesis of some monomeric half sandwich
ruthenium complexes containing O-alkylthiooxalate
ligands and dimeric ruthenium complexes containing
thiooxalate ligands.
to ruthenium. This band is similar to that found for
CpRu(PPh3)(CO)SCOPh (1961 cmꢀ1) [12].
The 1H NMR spectra of complexes 1–3 typically display
a singlet for the Cp protons at 4.56 and between 4.71–4.72
and 4.97–4.98 ppm. Variation associated with changing the
R group has negligible effects on the Cp-peaks in the NMR
spectra of these complexes. These data are in good agree-
ment with those reported for similar systems
(CpRu(L)(L0)SCOR [12], CpRu(L)(L0)SR [15,16]).
The 31P NMR spectra of 1–3 reflect changes in the
ligand type around ruthenium. For complexes 1 and 2 a
singlet is observed between 46.57–46.59 ppm and 86.19–
86.30 ppm, respectively, for the two identical phosphorus
atoms. The strong p-acid ligand (CO) in 3 deshields the
PPh3 phosphorus atom (55.68–55.76 ppm), compared to
2. Results and discussion
2.1. Synthesis
The ruthenium complexes CpRu(L)(L0)SCOCO2R (1–3)
are readily prepared by condensation of the hydrosulfido
complexes CpRu(L)(L0)SH with O-alkyl oxalyl chlorides
as shown in the following equation:
1
that of 1, similar to the Cp peak in the H NMR spectra
of 3 (vide supra). The 31P NMR data are comparable to
those reported for thiolate and thiocarboxylate ruthenium
species [12,15,16].
O
O
The reaction of CpRu(L)(L0)SH with oxalyl chloride in
a 2:1 molar ratio results in the formation of the ruthenium
dimers [CpRu(L)(L0)SCO]2 (4–6) as shown in the following
equation:
-HCl
RO
Ru
L'
+
OR
Ru
L'
Cl
L
SH
L
S
O
O
O
L = L´ = PPh3 (1), dppe (2); L= PPh3, L′ = CO (3)
R = Me (a), Et (b)
L
O
-HCl
Cl
L'
Ru
L'
2
S
Ru
L'
+
Cl
S
Ru
L
SH
L
O
ð1Þ
Complexes 1–3 are yellow to orange colored solids and
O
were identified by IR, 1H, 31P NMR spectroscopy, elemen-
tal analysis and X-ray structure determination for 1a and
2b. These new complexes are soluble in common organic
solvents and insoluble in hydrocarbons. They are quite sta-
ble as solids and in solution. There is no need for a base to
be added for these reactions to remove the produced HCl
indicating of the robustness of the products toward hydro-
lysis with HCl.
L = L´ = PPh3 (4), dppe (5); L= PPh3, L′= CO (6)
ð2Þ
Complexes 4–6 were characterized by IR, 1H, 31P NMR
spectroscopy and elemental analysis. As expected, the IR
spectra of 4–6 display characteristic bands in the range of
1721–1743 cmꢀ1 which can be assigned to the stretching
vibrations of the thiocarboxylate CO group. The vibration
of each of these complexes is shifted to higher wavenum-
bers in comparison to the analogous typical band for 1–
3. Complex 6 shows another strong absorption at
1967 cmꢀ1 for the terminal carbonyl group in its IR spec-
trum. This band is similar to those observed for 3. The
1H NMR spectra of 4, 5 and 6 show a singlet for the Cp
ring protons comparable to the analogous peak for 1–3,
respectively. The 31P NMR spectra of 4–6 display a singlet
at 46.19, 86.19 and 55.57 ppm, respectively. These peaks
are similar to those of 1, 2 and 3.
The IR spectra of the newly prepared complexes 1–3
show two medium bands in the ranges of 1720–1730 cmꢀ1
(OC@O) and 1580–1611 cmꢀ1 (SC@O) for the ketonic car-
bonyl groups of the O-alkylthiooxalato ligands. Although
the OC@O frequencies for complexes 1–3 are comparable
to each other, the mSC@O frequencies in these complexes
are sensitive to the ligands coordinated to the Ru center
(L and L0). For 1, the mSC@O vibration is in the range of
1580–1581 cmꢀ1, which is lower than that of 2 (1590–
1591 cmꢀ1) and this is lower than that of 3 (1609–
1611 cmꢀ1). These ligand-dependent frequencies are also
found in the thiocarboxylate analogs [12] and may be due
to a less electron density around the ruthenium in 3, com-
pared to that of 1 and 2. This can nicely be reflected by
the CO vibrations. Each of these ranges is lower than the
corresponding range reported for the thiocarboxylate
2.2. Crystal structures of 1a and 2b
Perspective views, together with the atomic numbering
schemes, of CpRu(PPh3)2SCOCO2Me (1a) and CpRu(dp-
pe)SCOCO2Et (2b) are shown in Figs. 1 and 2, respectively.
analogs (CpRu(L)(L0)SCOR: L = L0 = PPh3 (1598–
Selected bond lengths (A) and bond angles (ꢁ) of these com-
˚
ꢀ1
1610 cmꢀ1), dppe (1595–1624 cm ); L = PPh3, L0 = CO
plexes are summarized in Table 1. The coordination around
ruthenium in both complexes confirms to a typical piano
stool structure in which the Cp ring is bonded to ruthenium
1
2
(1636 cmꢀ1)) [12]. The spectra of 3 also contain a strong
band at 1967 cmꢀ1 for the terminal carbonyl group bonded

M. El-khateeb et al. / Journal of Organometallic Chemistry 691 (2006) 3743–3748
3745
˚
1a (average 2.3374 A) are similar to those of thiolate ana-
logs [17,18]. However, the analogous Ru–P bond distances
˚
of 2b (2.2772(6), 2.2527(6) A) which are also comparable to
˚
those of CpRu(dppm)SCOCH2Ph (2.2534(9), 2.2867(9) A)
[12] are shorter than those of 1a. This trend is normal for
complexes containing two triphenylphosphine ligands com-
pared to those having only one diphosphine ligand. The
˚
(S)C@O bond lengths of 1.224(3) A for 2b is clearly longer
˚
than the (O)C@O (1.206(3) A) length in the same molecule.
However, for 1a the situation is somewhat different; for one
molecule these C@O bond lengths are almost equal
˚
[(S)C@O: 1.210(7) vs. (O)C@O (1.209(9) A)] while for the
other the (O)C@O distance is longer than the (S)C@O
˚
[(S)C@O: 1.202(7) vs. (O)C@O (1.234(9) A)]. The corre-
sponding (S)C@O bond length of CpRu(dppm)SCOCH2Ph
˚
is 1.211(4) A [12].
3. Experimental
All synthetic operations were carried out under nitrogen
atmosphere using Schlenk line techniques. Tetrahydrofuran
(THF), diethyl ether and hexane were dried and distilled
over sodium/benzophenone. Complexes CpRu(L)(L0)SH
were prepared according to reported procedures [9–11].
O-alkyl oxalyl chlorides, oxalyl chloride and ruthenium
chloride trihydrate were obtained from ACROS and used
without further purification. Infrared spectra were recorded
on a Bruker 410 FT-IR spectrophotometer in CH2Cl2 solu-
1
tions using NaCl windows. H and 31P NMR spectra were
recorded using a Bruker AVANCE 400 MHz spectrometer.
Chemical shifts are quoted in ppm downfield of TMS and
referenced using the chemical shifts of residual solvent
resonances. Elemental analyses were performed by the
Institute of Organic and Macromolecular Chemistry,
FSU-Jena. Melting points were recorded on a Stuart Melt-
ing point apparatus and are uncorrected.
3.1. General procedure for the preparation of
CpRu(L)(L0)SCOCO2R (1 and 2)
The respective hydrosulfido ruthenium complexes
CpR(L)(L0)SH (0.50 mmol) were dissolved in 15.0 mL of
THF in a Schlenk tube and were cooled to ꢀ78 ꢁC. A
THF-solution of methyl- or ethyl oxalyl chloride
(0.52 mmol) was added dropwise at the same temperature.
The resulting mixture was stirred for 30 min at this temper-
ature. The volume of the solution was concentrated under
vacuum at room temperature to about 2.0 mL and was
introduced to a silica gel column made up in hexane. Elu-
tion with hexane removed the excess O-alkyl oxalyl chlo-
ride, and with (1:1 v:v) ratio of diethyl ether:hexane gave
a yellow band of the products which was collected, dried
and recrystallized from THF/hexane.
Fig. 1. ORTEP drawing of CpRu(PPh3)2SCOCO2Me (1a).
in an g5-fashion. The geometry of the CpRu(L)(L0) moiety
is similar to that observed for other related complexes [15–
18]. The Ru–S bond distances of 1a (2.3930(12),
˚
˚
2.3940(13) A) and of 2b (2.3768(6) A) are slightly shorter
than those of known Ru-thiolato complexes, e.g.,
˚
CpRu(PPh3)2SC„CPh (2.4216(7) A) [17] and CpRu-
i
˚
ðPPh3Þ2SSiPr3 (2.462(3) A) [18]. However, these Ru–S bond
3.1.1. CpRu(PPh3)2SCOCO2Me (1a)
Yellow crystals (90%). m.p.: 105–106 ꢁC. IR (CH2Cl2,
distances are similar to that reported for CpRu(dppm)S-
cmꢀ1): mOC@O 1725 (m); mSC@O 1581 (m). 1H NMR
˚
COCH2Ph (2.3819(10) A) [12]. The Ru–P bond lengths in

3746
M. El-khateeb et al. / Journal of Organometallic Chemistry 691 (2006) 3743–3748
Fig. 2. ORTEP drawing of CpRu(dppe)SCOCO2Et (2b).
Table 1
˚
Selected bond length (A) and selected bond angles (ꢁ) of CpRu(PPh3)2SCOCO2Me (1a) and CpRu(dppe)SCOCO2Et (2b)
1a
2b
Ru1–C1
Ru1–C2
Ru1–C3
Ru1–C4
Ru1–C5
Ru1–P1
Ru1–P2
Ru1–S1
S1–C42
C42–O1
C43–O2
C42–C43
C43–O3
C44–O3
2.228(5)
2.225(5)
2.218(5)
2.220(4)
2.230(5)
2.3395(12)
2.3356(12)
2.3930(12)
1.716(6)
1.202(7)
1.234(9)
1.539(10)
1.213(9)
1.526(10)
Ru2–C45
Ru2–C46
Ru2–C47
Ru2–C48
Ru2–C49
Ru2–P3
Ru2–P4
Ru2–S2
S2–C86
C86–O4
C87–O5
C86–C87
C87–O6
C88–O6
2.225(5)
2.225(5)
2.213(5)
2.218(4)
2.232(5)
2.3359(12)
2.3409(12)
2.3940(13)
1.707(6)
1.210(7)
1.209(9)
1.544(9)
1.217(9)
1.493(10)
Ru–C1
Ru–C2
Ru–C3
Ru–C4
Ru–C5
Ru–P1
2.251(2)
2.246(2)
2.201(2)
2.201(2)
2.228(2)
2.2772(6)
2.2527(6)
2.3768(6)
1.717(2)
1.224(3)
1.206(3)
1.544(3)
1.334(3)
1.456(3)
Ru–P2
Ru–S1
S1–C32
C32–O1
C33–O3
C32–C33
C33–O3
C34–O3
P1–Ru1–P2
P1–Ru1–S1
P2–Ru1–S1
98.80(4)
91.76(4)
91.42(5)
115.1(2)
116.2(6)
130.8(5)
123.8(9)
112.5(5)
111.3(8)
119.9(8)
40.1(10)
P3–Ru2–P4
P3–Ru2–S2
P4–Ru2–S2
98.82(4)
91.69(4)
91.42(5)
115.1(2)
114.9(6)
130.9(5)
123.2(9)
113.3(5)
112.3(9)
119.9(8)
38.1(11)
P1–Ru–P2
P1–Ru–S1
P2–Ru–S1
82.91(2)
83.03(2)
91.55(2)
111.90(8)
119.5(2)
128.84(18)
124.6(2)
111.64(16)
118.28(18)
110.26(19)
ꢀ178.6(2)
C42–S1–Ru1
O1–C42–C43
O1–C42–S1
O2–C43–O3
C43–C42–S1
C43–O3–C44
O2–C43–C42
O1–C42–C43–O2
C86–S2–Ru2
O4–C86–C87
O4–C86–S2
O5–C87–O6
C87–C86–S2
C87–O6–C88
O5–C87–C86
O4–C86–C87–O5
C32–S1–Ru
O1–C32–C33
O1–C32–S1
O2–C33–O3
C33–C32–S1
C33–O2–C34
O2–C33–C32
O1–C32–C33–O3
(CDCl3): d 3.74 (s, 3H, CH3); 4.56 (s, 5H, C5H5); 7.12 (m,
30H, PPh3). 31P NMR (CDCl3): d 46.59. Anal. Calc. for
C44H40O3P2RuS Æ 0.5THF: C, 65.31; H, 5.00; S, 3.79.
Found: C, 64.80; H, 5.29; S, 3.71%.
3.1.2. CpRu(PPh3)2SCOCO2Et (1b)
Yellow crystals (87%). m.p.: 100–102 ꢁC. IR (CH2Cl2,
cmꢀ1): mOC@O 1720 (m); mSC@O 1580 (m). 1H NMR
(CDCl3): d 1.33 (t, 3H, CH3); 4.19 (q, 2H, CH2); 4.56 (s,

M. El-khateeb et al. / Journal of Organometallic Chemistry 691 (2006) 3743–3748
3747
5H, C5H5); 7.14 (m, 30H, PPh3). 31P NMR (CDCl3): d
46.57. Anal. Calc. for C45H40O3P2RuS Æ 2THF: C, 65.76;
H, 5.83; S, 3.31. Found: C, 64.84; H, 5.27; S, 3.46%.
2H, CH2PPh2); 2.73 (m, 2H, CH2PPh2); 4.72 (s, 5H,
C5H5); 7.29 (m, 12H, PPh2); 7.44 (m, 8H, PPh2). 31P
NMR (CDCl3): d 86.16. Anal. Calc. for C32H29OPRuS:
C, 61.53; H, 4.68; S, 5.13. Found: C, 60.91; H, 4.28; S,
4.90%.
3.1.3. CpRu(dppe)SCOCO2Me (2a)
Yellow crystals (85%). m.p.: 191–193 ꢁC. IR (CH2Cl2,
cmꢀ1): mOC@O 1724 (m); mSC@O 1591 (m). 1H NMR
(CDCl3): d 2.54 (m, 2H, CH2PPh2); 2.77 (m, 2H,
CH2PPh2); 3.71 (s, 3H, CH3); 4.71 (s, 5H, C5H5); 7.17
(m, 12H, PPh2); 7.31 (m, 8H, PPh2). 31P NMR (CDCl3):
d 86.30. Anal. Calc. for C34H32O3P2RuS: C, 59.73; H,
4.72; S, 4.69. Found: C, 58.91; H, 4.82; S, 4.22%.
3.2.3. [CpRu(PPh3)(CO)SCO]2 (6)
Orange crystals (60%). m.p.: 65–66 ꢁC. IR (CH2Cl2,
1
cmꢀ1): mC„O 1967 (s); mSC@O 1726 (m). H NMR (CDCl3):
d 4.98 (s, 5H, C5H5); 7.38 (m, 15H, PPh3). 31P NMR
(CDCl3): d 55.77. Anal. Calc. for C25H20O2PRuS: C,
58.13; H, 3.90; S, 6.21. Found: C, 57.50; H, 3.78; S, 6.00%.
3.1.4. CpRu(dppe)SCOCO2Et (2b)
3.3. Crystallographic analysis of CpRu(PPh3)2SCOCO2Me
(1a) and CpRu(dppe)SCOCO2Et (2b)
Yellow crystals (83%). m.p.: 181–182 ꢁC. IR (CH2Cl2,
cmꢀ1): mOC@O 1720 (m); mSC@O 1592 (m). 1H NMR
(CDCl3): d 1.42 (t, 3H, CH3); 2.43 (m, 2H, CH2PPh2);
2.76 (m, 2H, CH2PPh2); 4.30 (q, 2H, CH2); 4.72 (s, 5H,
C5H5); 7.19 (m, 12H, PPh2); 7.32 (m, 8H, PPh2). 31P
NMR (CDCl3): d 86.19. Anal. Calc. for C35H34O3P2RuS:
C, 60.25; H, 4.90; S, 4.60. Found: C, 59.96; H, 5.02; S,
4.23%.
The crystal data are shown in Table 2. Data for 1a and
2b were collected on an Oxford Gemini S diffractometer at
˚
100 K using Mo Ka radiation (k = 0.71073 A). Both struc-
tures were solved by direct methods using SHELXS-97 [19]
and refined by full-matrix least-square procedures on F o2
using SHELX-97 [20]. All non-hydrogen atoms were refined
anisotropically. The hydrogen atom positions have been
refined using the atom corresponded riding model. The
asymmetric unit of 1a comprises two independent mole-
cules together with two THF molecules as packing sol-
vents, each having an occupation factor of 0.5.
3.1.5. CpRu(PPh3)(CO)SCOCO2Me (3a)
Yellow crystals (80%). m.p.: 221–222 ꢁC. IR (CH2Cl2,
cmꢀ1): mC„O 1967 (s); mOC@O 1730 (m); mSC@O 1609 (m).
1H NMR (CDCl3): d 3.76 (s, 3H, CH3); 4.98 (s, 5H,
C5H5); 7.36 (m, 15H, PPh3). 31P NMR (CDCl3): d 55.68.
Anal. Calc. for C27H23O4PRuS: C, 56.34; H, 4.03; S,
5.57. Found: C, 56.26; H, 4.09; S, 5.26%.
3.1.6. CpRu(PPh3)(CO)SCOCO2Et (3b)
Table 2
Yellow crystals (75%). m.p.: 191–192 ꢁC. IR (CH2Cl2,
cmꢀ1): mC„O 1967 (s); mOC@O 1725 (m); mSC@O 1611 (m).
1H NMR (CDCl3): d 1.32 (t, 3H, CH3); 4.18 (q, 2H,
CH2); 4.97 (s, 5H, C5H5); 7.35 (m, 15H, PPh3). 31P NMR
(CDCl3): d 55.76. Anal. Calc. for C28H25O4PRuS: C,
57.04; H, 4.23; S, 5.44. Found: C, 56.81; H, 4.35; S, 5.09%.
Selected crystal data and refinement parameters for CpRu(PPh3)2SCO-
CO2Me (1a) and CpRu(dppe)SCOCO2Et (2b)
1a
2b
Empirical formula
Formula weight (g molꢀ1
Crystal size (mm)
Crystal system
C
845.87
0.3 · 0.2 · 0.2
Triclinic
46H42O3.5P2RuS
C35H34O3P2RuS
697.69
0.2 · 0.1 · 0.05
Monoclinic
P2(1)/c
)
ꢀ
Space group
P1
3.2. General procedure for the preparation of
[CpRu(L)(L0)SCO]2 (4–6)
3
˚
Volume (A )
4282(1)
4
3135.6(5)
4
Z
Unit cell dimensions
˚
These complexes were prepared in a similar way to that
used for the preparation of 1–3 (Section 3.1). Oxalyl chlo-
ride (0.25 mmol) was used. The products were eluted with
pure diethyl ether.
a (A)
12.932(1)
14.753(3)
26.124(4)
75.367(1)
75.703(7)
64.026(6)
ꢀ15 6 k 6 15
ꢀ18 6 k 6 18
ꢀ32 6 l 6 32
Mo Ka
1.312
0.529
2.90–26.06
0.71073
0.0485
11.6283(11)
23.0039(17)
12.8614(12)
90
114.299(9)
90
ꢀ13 6 h 6 13
ꢀ27 6 k 6 27
ꢀ15 6 l 6 15
Mo Ka
1.478
0.703
3.17–25.20
0.71073
0.0242
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
d (ꢁ)
Index range
3.2.1. [CpRu(PPh3)2SCO]2 (4)
Yellow crystals (73%). m.p.: 95–96 ꢁC. IR (CH2Cl2,
1
cmꢀ1): mSC@O 1721 (m). H NMR (CDCl3): d 4.68 (s, 5H,
C5H5); 7.41 (m, 30H, PPh3). 31P NMR (CDCl3): d 46.57.
Anal. Calc. for C42H35OPRuS: C, 67.19; H, 4.70; S, 4.27.
Found: C, 66.93; H, 5.02; S, 3.89%.
Radiation type
Density (Mg mꢀ3
)
l (mmꢀ1
h (ꢁ)
)
˚
k (A)
R[F2 > 2r(F2)]
3.2.2. [CpRu(dppe)SCO]2 (5)
Orange crystals (64%). m.p.: 166–167 ꢁC. IR (CH2Cl2,
xR(F2)a
0.1547
0.0443
2
a
x ¼ 1=½r2ðF o2Þ þ ð0:1007PÞ ꢁ where P ¼ ðF o2 þ 2F 2c Þ=3.
cmꢀ1): mSC@O 1743 (m). 1H NMR (CDCl3): d 2.50 (m,

3748
M. El-khateeb et al. / Journal of Organometallic Chemistry 691 (2006) 3743–3748
[3] D.A. Dobbs, R.B. Bergman, Inorg. Chem. 33 (1994) 5329.
Acknowledgements
[4] M. Casado, M. Ciriano, A. Edwards, F. Lahoz, L. Oro, J. Perez-
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(2001) 293.
We thank the Deanship of Research, Jordan University
of Science and Technology and Shoman Foundation for
financial support.
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Appendix A. Supplementary materials
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre (Deposition
Nos. CCDC 600974 and 600975) for compounds 1a and
2b, respectively. Copies of this information can be obtained
free of charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: +44 1233 336 033; e-mail:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.
ac.uk). Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2006.05.018.
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