One-pot synthesis of ruthenium metallacycles via oxidative addition of diaryldichalcogen and halogen across a ru-ru bond

Article abstract of DOI:10.1021/om400686q

Oxidative addition of diaryldichalcogen ligands (REER) to ruthenium carbonyl (Ru₃(CO)₁₂) followed by the addition of halogen (X₂) afforded chalcogen-bridged Ru(II)-based metallacycles of general formula [X(CO)₃Ru(μ-ER)₂Ru(CO)₃X] (1-10), where E = S, Se, and Te; R = phenyl, tolyl, and benzyl; and X = Br and I. Compounds 1-10 were characterized using IR, UV-vis, and NMR spectroscopic techniques. Molecular structures of the metallacycles have been elucidated by single-crystal X-ray diffraction methods that confirm the dimeric nature of metallacycles, wherein the two Ru(CO)₃X moieties are held together by the bridging aryl chalcogenide ligands.

Full text of DOI:10.1021/om400686q

Article
pubs.acs.org/Organometallics
One-Pot Synthesis of Ruthenium Metallacycles via Oxidative
Addition of Diaryldichalcogen and Halogen across a Ru−Ru Bond
R. Nagarajaprakash,† Buthanapalli Ramakrishna,† K. Mahesh,† Shaikh M. Mobin,‡ and Bala. Manimaran*,†
†Department of Chemistry, Pondicherry University, Puducherry, 605014, India
‡National Single Crystal X-ray Diffraction Facility, Indian Institute of Technology-Bombay, Powai, Mumbai, 400076, India
S
* Supporting Information
ABSTRACT: Oxidative addition of diaryldichalcogen ligands
(REER) to ruthenium carbonyl (Ru3(CO)12) followed by the
addition of halogen (X2) afforded chalcogen-bridged Ru(II)-
based metallacycles of general formula [X(CO)3Ru(μ-ER)2Ru-
(CO)3X] (1−10), where E = S, Se, and Te; R = phenyl, tolyl,
and benzyl; and X = Br and I. Compounds 1−10 were
characterized using IR, UV−vis, and NMR spectroscopic techniques. Molecular structures of the metallacycles have been
elucidated by single-crystal X-ray diffraction methods that confirm the dimeric nature of metallacycles, wherein the two
Ru(CO)3X moieties are held together by the bridging aryl chalcogenide ligands.
with addition across the Ru−Ru bond afforded the
chalcogenide-bridged dinuclear ruthenium metallacycles 1−
10. When ruthenium carbonyl was treated with diary-
ldichalcogenide, a Ru−Ru bond containing intermediate,
[Ru2(CO)6(μ-ER)2], is expected to form.9 Addition of halogen
(Br2/I2) to the solution of [Ru2(CO)6(μ-ER)2] resulted in
cleavage of the Ru−Ru bond with formation of a metal−
halogen bond to afford [X(CO)3Ru(μ-ER)2Ru(CO)3X]. It is
worthwhile to mention that halogen addition to the ruthenium
metal center takes place predominantly in cis fashion.
To support our assumption that [Ru2(CO)6(μ-ER)2] is
indeed formed as an intermediate, a control reaction was
carried out by reacting Ru3(CO)12 and diphenyldiselenide in
mesitylene medium at 80 °C for 8 h. The IR spectrum of the
product formed in this reaction displayed six bands at ν(CO)
2081(s), 2053(s), 2008(s), 2005(s), 1994(m), and 1963(w)
cm−1, which were matching characteristically with that of the
reported compound, [Ru2(CO)6(μ-SePh)2].9 This compound
was isolated, and Br2 was added at 5 °C. The IR spectrum of
the brominated compound was identical with that of [Br-
(CO)3Ru(μ-SePh)2Ru(CO)3Br] (5). This observation sup-
ports the proposed reaction pathway and aids in proving the
Ru−Ru-bonded intermediate [Ru2(CO)6(μ-ER)2] formation at
the initial stage, which probably allowed halogen (Br2/I2) to
add from the same side, resulting in cis orientation of halides in
the metallacycles.
INTRODUCTION
■
Although oxidative addition of chalcogen atoms to a ruthenium
metal center to form ruthenium chalcogenide cluster
compounds is known in the literature, reports involving
Ru3(CO)12 and diaryl dichalcogenides are relatively rare.1−7
Schermer and Baddley reported the reaction of Ru3(CO)12 with
PhEEPh (E = Se, Te) to afford a mixture of [Ru2(CO)6(μ-
EPh)2] and [Ru(CO)2(μ-EPh)]n.8 Later, Andreu et al. reported
structural evidence for a Ru−Ru bond containing complex,
[Ru2(CO)6(μ-SePh)2].9 Research groups of Deeming and
Leong demonstrated the reactions of Ph2Se2/Ph2Te2 with
[Os3(CO)10(CH3CN)2] to obtain an isomeric mixture of
chalcogen-bridged triosmium clusters.10,11 Several complexes
derived from ruthenium carbonyl and dichalcogenides were of
structural complexity and mostly stabilized with phosphine
ligands.12−17 Recently, we have intended to synthesize
chalcogen-bridged diruthenium complexes of high symmetry
that are stabilized with halogens (Br, I). A metallacycle with
symmetric structure is desirous to extend the dinuclear complex
toward the synthesis of multinuclear metallacyclophanes.
Herein, we report on the oxidative addition reaction of
diaryldichalcogen ligands (REER) and Br2/I2 with Ru3(CO)12
to give diruthenium metallacycles of general formula [X-
(CO)3Ru(μ-ER)2Ru(CO)3X] (1−10) and their structural
features.
Better reactivity was noticed for the reaction of Ru3(CO)12
with selenido/tellurido ligands than sulfido ligands. A decline in
E−E bond energies on descending from S to Te may be
reasoned for the observed reactivity. All the dinuclear
ruthenium metallacycles were crystallized in common organic
solvents such as CH2Cl2 and acetone by slow evaporation at
RESULTS AND DISCUSSION
■
A series of chalcogen (S, Se, Te)-bridged diruthenium
metallacyclic compounds [X(CO)3Ru(μ-ER)2Ru(CO)3X]
(1−10) (E = S, Se, and Te; R = phenyl, tolyl, and benzyl; X
= Br and I) were synthesized by the reaction of diary-
ldichalcogen and halogen (Br, I) to rudimentary ruthenium
carbonyl (Ru3(CO)12) in a one-pot reaction under facile
conditions (Scheme 1). The formal oxidative cleavage of the
E−E bond of diaryldichalcogen and the X−X bond of halogen
Received: July 13, 2013
Published: November 27, 2013
© 2013 American Chemical Society
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Scheme 1. Synthesis of Chalcogen-Bridged Dinuclear Ruthenium Metallacycles, [X(CO)3Ru(μ-ER)2Ru(CO)3X] (1−10)
room temperature, and the crystals were found to be air, light,
and moisture stable.
spectra of 1, 5, 6, 9, and 10 displayed two signals in the region δ
175−191 ppm in a 1:2 ratio for the axial and equatorial
carbonyl carbons and four signals in the region δ 135−107 ppm
for ipso, ortho, meta, and para carbons of the phenyl ring
attached to the chalcogenide ligand.
The molecular structures of metallacycles [X(CO)3Ru(μ-
ER)2Ru(CO)3X] 1, 4−7, 9, and 10 were determined by single-
crystal X-ray diffraction methods, which confirm their dimeric
structure, wherein two Ru(CO)3X moieties are bridged by two
chalcogenide ligands (Figures S1−S6). The metallacycles have
isostructural features, though they have crystallized in different
space groups. Metallacycles 1, 5, and 6 crystallized in
monoclinic space groups such as C2/c, P21/n, and P21/c,
respectively, while 9 and 10 both crystallized in triclinic space
The compounds 1−10 have been characterized using IR,
UV−vis, 1H and 13C NMR spectroscopic techniques, and
elemental analyses. IR spectra of the compounds 1−10
displayed strong bands in the region of ν(CO) 1950 to 2025
cm−1 with similar patterns for the terminal carbonyl groups.7
The terminal carbonyl stretching frequency shifted toward the
lower energy side as we go from S-, to Se-, to Te-bridged
compounds. This observation is attributed to the fact that the
back-bonding from the ruthenium metal center to the π*
orbital of the CO group is more pronounced in the case of Te-
bridged compounds than that of Se-bridged compounds, which
in turn is more than that of S-bridged compounds, owing to
their basicity decreasing from Te to S (Table 1, comparison of
group P1 (Table S1). A representative ORTEP diagram of 10 is
̅
shown in Figure 1. The central core of the metallacycles
Table 1. Comparison of IR Stretching Frequencies of
Terminal CO Groups
compound
ν(CO) (cm−1
)
1
2125(s)
2116(s)
2116(s)
2114(s)
2111(s)
2118(s)
2112(s)
2107(s)
2103(s)
2096(s)
2071(s)
2063(s)
2056(s)
2055(s)
2050(s)
2046(s)
2043(s)
2042(s)
2038(s)
2037(s)
2026(sh)
1996(sh)
1997(sh)
1997(sh)
1993(sh)
5
6
9
10
1, 5, and 9; 6 and 10). The halide bonded to the metal center
also influences the metal to CO back-bonding. The terminal
CO stretching frequencies of Br-substituted compounds
appeared in the higher energy side compared to iodine-
substituted ones, indicating that iodine favors Ru−CO back-
bonding more than bromine (Table 1, comparison of 5 and 6;
9 and 10).
1H and 13C NMR spectra of metallacycles supported the
1
formation of a single product in all reactions. H NMR spectra
Figure 1. ORTEP view of metallacycle [I(CO)3Ru(μ-TePh)2Ru-
(CO)3I] (10). Thermal ellipsoids are drawn at 40% probability.
displayed a doublet of doublets and two triplets in the range δ
7.60−7.30 ppm that were assigned to o-H, m-H, and p-H of the
phenyl ring, respectively, for the compounds [Br(CO)3Ru(μ-
SPh)2Ru(CO)3Br] (1), [Br(CO)3Ru(μ-TePh)2Ru(CO)3Br]
(9), and [I(CO)3Ru(μ-TePh)2Ru(CO)3I] (10). The 1H
NMR spectra of Se-bridged compounds [Br(CO)3Ru(μ-
SePh)2Ru(CO)3Br] (5) and [I(CO)3Ru(μ-SePh)2Ru(CO)3I]
(6) showed a multiplet due to m-H and p-H of the phenyl ring
in the range δ 7.40−7.35 ppm, along with a doublet of doublets
for o-H that appeared in the range δ 7.64−7.60 ppm. 13C NMR
consists of a Ru2E2 four-membered ring. The Ru2E2 core
contains two ruthenium centers in an octahedral geometry,
wherein each ruthenium is surrounded by three terminal
carbonyl groups, two bridging chalcogen atoms, and a halogen.
The phenyl substituents attached to the chalcogen atoms are
oriented in a cis fashion. Similarly, the halide ligands bonded to
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ruthenium centers are predominantly cis positioned to each
other, while trans positioned with respect to the aryl rings.
The Ru(1)−Ru(2) nonbonding distance in 1 is found to be
∼3.646 Å. The Ru−S−Ru bridging bond angle in 1 is
96.71(4)°, which is comparable to the reported compound
[Ru2(CO)4(μ-SPh)2I2(PMe3)2].18 This bridging bond angle is
larger than the bond angles in metal−metal bond containing
compounds in the literature.7 Reactions of Ru3(CO)12 with
Ph2Se2/Ph2Te2 ligands were reported by Schermer and
Baddley, and the crystal structure of [Ru2(μ-SePh)2(CO)6]
confirmed the presence of a metal−metal bond.8,9 In [Ru2(μ-
SePh)2(CO)6], the Ru2Se2 framework is found to have a
butterfly conformation with a torsional angle of 97.8°. In the
present work, the metal−metal bond has been cleaved by
oxidative addition of bromine/iodine. As a consequence, there
is a large decrease in torsional angle of the Ru2Se2 framework
(Table 2, comparison of 5 and 6), and so the structure is nearly
CONCLUSION
■
We have demonstrated the successful synthesis of ruthenium-
(II)-based dinuclear metallacycles with bridging chalcogen-
containing ligands via oxidative addition of diaryldichalcogenide
and halogen ligands to ruthenium carbonyl. Halogen addition
at the intermediate stage stabilized the metallacycle with Ru(II)
in the final product. Addition of halogen on ruthenium centers
predominantly resulted in a cis fashion with cleavage of the
Ru−Ru bond. The crystal structures of seven compounds are
isostructural, having similar structural features. The synthetic
methodology offers an effective and comparatively expedient
route to synthesize stable ruthenium metallacycles of higher
nuclearity. We are currently exploiting the one-pot reaction
strategy for the design of novel metallacyclophanes using rigid
and flexible ditopic linkers.
EXPERIMENTAL SECTION
■
General Details. All manipulations were carried out under a dry,
oxygen-free N2 atmosphere using standard Schlenk techniques.
Ru3(CO)12 was purchased from Strem Chemicals Inc. All diary-
ldichalcogen ligands were purchased from Sigma Aldrich. The solvents
were purified using standard methods and freshly distilled prior to use.
IR spectra were recorded on a Nicolet-6700 FT-IR spectrophotometer.
Electronic absorption spectra were obtained on an Ocean Optics HR
Table 2. Comparison of Torsional Angles (deg) and M···M
Distances (Å)
torsional
angle
Ru···Ru
distance
compound
1
S(1)#1−Ru(1)−S(1)−Ru(1)#
Se(2)−Ru(2)−Se(1)−Ru(1)
Se(2)−Ru(2)−Se(1)−Ru(1)
Te(2)−Ru(1)−Te(1)−Ru(2)
Te(2)−Ru(1)−Te(1)−Ru(2)
16.64
10.91
9.53
3.646
3.795
3.811
4.032
4.040
5
4000 spectrophotometer. H and 13C NMR spectra were recorded on
1
6
a Avans Bruker 400 MHz spectrometer. Elemental analyses were
performed in an Elementar Vario ELIII elemental analyzer.
9
11.40
10.54
10
Crystallographic Structure Determination. Single-crystal X-ray
structural studies of 1 were performed on an Oxford Diffraction
XCALIBUR-EOS CCD equipped diffractometer, while those of 4, 6, 7,
9, and 10 were performed on an Oxford Diffraction XCALIBUR-S
CCD equipped diffractometer with an Oxford Instrument low-
temperature attachment. Crystal data were collected at 300 K for 1
using graphite-monochromated Mo Kα radiation (λα = 0.7107 Å). For
4, 6, 7, 9, and 10 crystal data were collected at 150(2) K using
graphite-monochromated Mo Kα radiation (λα = 0.71073 Å). The
strategy for the data collection was evaluated using the CrysAlisPro
CCD software. Crystal data were collected by standard “phi-omega
scan” techniques and were scaled and reduced using CrysAlisPro RED
software. The structures were solved by direct methods using
SHELXS-97 and refined by full matrix least-squares with SHELXL-
97 refining on F2.19−21 The positions on all the atoms were obtained
by direct methods. All non-hydrogen atoms were refined anisotropi-
cally. The hydrogen atoms were placed in geometrically constrained
positions and refined with isotropic temperature factors, generally
1.2Ueq of their parent atoms.
planar. The bond angles Ru(1)−Se(1)−Ru(2) and Ru(1)−
Se(2)−Ru(2) are 95.70(4)° and 95.90(4)° in 5 and 96.22(3)°
and 96.28(3)° in 6, whereas in [Ru2(μ-SePh)2(CO)6], the
respective bond angles were reported as 64.8(1)° and 64.7(1)°
(Table S2). The Ru(1)−Se(1), Ru(1)−Se(2), Ru(2)−Se(1),
and Ru(2)−Se(2) bond distances of 2.564(14), 2.555(14),
2.554(14), and 2.554(14) Å in 5 and 2.560(7), 2.557(8),
2.559(8), and 2.561(7) Å in 6, respectively, are somewhat
longer than in [Ru2(μ-SePh)2(CO)6]. The decrease in torsion
angle of the Ru2Se2 framework and increase in the bond angles
and bond lengths in 5 and 6 indicate that the Ru2Se2 framework
is not as puckered as found in [Ru2(μ-SePh)2(CO)6] and the
geometry around the Ru atom switches from a distorted
octahedral to a nearly regular octahedral geometry with less
strain. The bond angles around the Ru center in 5, C(1)−
Ru(1)−C(3), C(1)−Ru(1)−C(2), C(3)−Ru(1)−C(2), C(1)−
Ru(1)−Br(1), C(2)−Ru(1)−Se(2), and C(3)−Ru(1)−Se(1),
of 95.2(5)°, 96.1(5)°, 91.5(5)°, 178.0(3)°, 170.2(4)°, and
172.5(4)° clearly indicate that the octahedral geometry around
the Ru center is not as distorted as in [Ru2(μ-SePh)2(CO)6].
The torsional strain in the Ru2E2 core is found to increase as
the size of the bridging atom increases from S through Se to Te
as expected generally. The torsional angles of the compounds
are listed in Table 2. The torsional strain in the four-membered
ring is less in iodo compounds than in their bromo analogues.
The Ru···Ru nonbonding distance is found to increase as the
size of the bridging atom increases. The Ru···Ru distance in
iodo compounds is slightly longer than their bromo analogues,
and due to this reason, ring strain is less in iodo compounds
than that of bromo compounds. Comparison of 5 with 6 and 9
with 10 is given in Table 2.
Synthesis of [Br(CO)3Ru(μ-SPh)2Ru(CO)3Br] (1). A mixture of
Ru3(CO)12 (0.1 mmol) and diphenyldisulfide (0.15 mmol) in
mesitylene was stirred at 80 °C. After 1 h, the yellow transparent
solution turned a red color, and stirring was continued for 8 h. The
reaction mixture was allowed to reach room temperature gradually and
cooled to 5 °C using an ice bath. Bromine (0.2 mmol) was added to
the clear reaction mixture at 5 °C, resulting in the formation of an
orange-colored precipitate. The reaction mixture was stirred for 2 h at
room temperature. The product was filtered off from a mesitylene
solution and washed with hexane. Yield: 44 mg, 59.6%. IR (CH2Cl2):
1
ν(CO) 2125(s), 2118(s), 2071(s), 2046(s), 2026(sh) cm−1. H NMR
(400 MHz, CDCl3, ppm): δ 7.64 (d, 2H, o-H, ph), 7.41 (t, 2H, m-H,
ph) 7.35 (t, 1H, p-H, ph). 13C NMR (100 MHz, CDCl3, ppm): δ
189.7, 183.4 (1:2 CO), 135.1 (i-C, ph), 131.3 (o-C, ph), 129.9 (m-C,
ab
ph), 128.5 (p-C, ph). UV−vis {(CH2Cl2)/λmax (nm)}: 262, 291.
Anal. Calcd for C18H10Br2O6Ru2S2: C, 28.89; H, 1.35. Found: C,
28.94; H, 1.32.
Synthesis of [Br(CO)3Ru(μ-SC6H4CH3)2Ru(CO)3Br] (2). Metallacycle
2 was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), p-tolyldisulfide (0.15 mmol), and bromine
(0.2 mmol), and the compound was obtained as an orange solid. Yield:
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49 mg, 64%. IR (CH2Cl2): ν(CO) 2125(s), 2117(s), 2070(s), 2045(s),
2004(sh) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.27 (m, 4H, o-
and m-H, ph), 2.37 (s, 3H, tolyl H). UV−vis {(CH2Cl2)/λmaxab (nm)}:
259, 273. Anal. Calcd for C20H14Br2O6Ru2S2: C, 30.94; H, 1.82.
Found: C, 30.92; H, 1.78.
13C NMR (100 MHz, CDCl3, ppm): δ 190.5, 179.2 (1:2, CO), 135.6
(o-C, ph), 129.1 (m-C, ph), 128.2 (p-C, ph), 107.8 (C1, ph). UV−vis
a b
{(CH2 Cl2 )/λm a x
(nm)}: 263, 296. Anal. Calcd for
C18H10Br2O6Ru2Te2: C, 23.01; H, 1.07. Found: C, 23.04; H, 1.08.
Synthesis of [I(CO)3Ru(μ-TePh)2Ru(CO)3I] (10). Metallacycle 10 was
synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), diphenylditelluride (0.15 mmol), and iodine
(0.2 mmol), and the compound was obtained as a red solid. Yield: 85
mg, 91.82%. IR (CH2Cl2): ν(CO) 2111(m), 2096(s), 2050(s), 2037(s),
1993(w) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.63 (dd, 2H, o-
H, ph), 7.38 (t, 1H, p-H, ph), 7.30 (t, 2H, m-H, ph). 13C NMR (100
MHz, CDCl3, ppm): δ 188.9, 179.9 (1:2 CO), 135.4 (o-C, ph), 129.0
Synthesis of [Br(CO)3Ru(μ-SCH2Ph)2Ru(CO)3Br] (3). Metallacycle 3
was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), dibenzyldisulfide (0.15 mmol), and bromine
(0.2 mmol), and the compound was obtained as an orange solid. Yield:
53 mg, 69.3%. IR (CH2Cl2): νCO 2123(s), 2117(s), 2068(s), 2051(s),
2006(sh) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.32 (m, 5H, o-,
ab
m-, and p-H, ph), 3.08 (s, 2H, benzyl H). UV−vis {(CH2Cl2)/λmax
ab
(nm)}: 251. Anal. Calcd for C20H14Br2O6Ru2S2: C, 27.60; H, 1.60.
Found: C, 27.62; H, 1.65.
(m-C, ph), 128.1 (p-C, ph), 109.5 (i-C, ph). UV−vis {(CH2Cl2)/λmax
(nm)}: 259, 305. Anal. Calcd for C18H10I2O6Ru2Te2: C, 20.92; H,
0.98. Found: C, 20.92; H, 1.01.
Synthesis of [I(CO)3Ru(μ-SCH2Ph)2Ru(CO)3I] (4). Metallacycle 4
was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), dibenzyldisulfide (0.15 mmol), and iodine
(0.2 mmol), and the compound was obtained as an orange solid. Yield:
56 mg, 74.2%. IR (CH2Cl2): ν(CO) 2119(s), 2110(s), 2062(s), 2034(s),
1996(sh) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.32 (m, 5H, o-,
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR spectroscopic characterization for compounds 2−4, 7,
and 8. ORTEP diagrams of compounds 1, 4−7, and 9.
Crystallographic data and structure refinement details of
compounds 1, 4−7, 9, and 10 and their selected bond lengths
and bond angles. Supramolecular interactions. CIF files giving
crystallographic data. This material is available free of charge via
the Internet at http://pubs.acs.org.
ab
m-, and p-H, ph), 4.09 (m, 2H, benzyl H). UV−vis {(CH2Cl2)/λmax
(nm)}: 249. Anal. Calcd for C20H14I2O6Ru2S2: C, 30.94; H, 1.82.
Found: C, 30.92; H, 1.85.
Synthesis of [Br(CO)3Ru(μ-SePh)2Ru(CO)3Br] (5). Metallacycle 5
was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), diphenyldiselenide (0.15 mmol), and bromine
(0.2 mmol), and the compound was obtained as an orange solid. Yield:
64 mg, 77%. IR (CH2Cl2): ν(CO) 2116(s), 2113(s), 2065(s), 2044(s),
2006(sh) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.64 (m, 2H, o-
H, ph), 7.38 (m, 3H, m-, and p-H, ph). 13C NMR (100 MHz, CDCl3,
ppm): δ 189.6, 181.5 (1:2 CO), 131.4 (o-C, ph), 129.0 (m-C, ph),
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: manimaran.che@pondiuni.edu.in.
ab
127.6 (p-C, ph), 127.0 (i-C, ph). UV−vis {(CH2Cl2)/λmax (nm)}:
Notes
257, 270. Anal. Calcd for C18H10Br2O6Ru2Se2: C, 25.67; H, 1.20.
Found: C, 25.64; H, 1.18.
The authors declare no competing financial interest.
Synthesis of [I(CO)3Ru(μ-SePh)2Ru(CO)3I] (6). Metallacycle 6 was
synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), diphenyldiselenide (0.15 mmol), and iodine
(0.2 mmol), and the compound was obtained as an orange solid. Yield:
67 mg, 72.6%. IR (CH2Cl2): ν(CO) 2116(s), 2106(s), 2056(s), 2042(s),
1997(sh) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.60 (m, 2H, o-
H, Ph), 7.38 (m, 3H, m- and p-H, ph). 13C NMR (100 MHz, CDCl3,
ppm): δ 188.7, 183.7 (1:2, CO), 132.2 (o-C, ph), 129.9 (m-C, ph),
ACKNOWLEDGMENTS
■
We thank the Council of Scientific and Industrial Research,
Government of India, and the Department of Science and
Technology, Government of India, for financial support. We are
grateful to the Central Instrumentation Facility, Pondicherry
University, for providing spectral data.
ab
129.3 (p-C, ph), 128.5 (i-C, ph). UV−vis {(CH2Cl2)/λmax (nm)}:
253, 345. Anal. Calcd for C18H10I2O6Ru2Se2: C, 23.09; H, 1.08. Found:
C, 23.06; H, 1.08.
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■
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Synthesis of [Br(CO)3Ru(μ-SeCH2Ph)2Ru(CO)3Br] (7). Metallacycle
7 was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), dibenzyldiselenide (0.15 mmol), and bromine
(0.2 mmol), and the compound was obtained as an orange solid. Yield:
62 mg, 65.26%. IR (CH2Cl2): ν(CO) 2123(s), 2114(s), 2064(s),
2012(m) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.33 (m, 5H, o-,
ab
m-, and p-H, ph), 3.91 (s, 2H, benzyl H). UV−vis {(CH2Cl2)/λmax
(nm)}: 249. Anal. Calcd for C20H14Br2O6Ru2Se2: C, 27.60; H, 1.60.
Found: C, 27.62; H, 1.56.
Synthesis of [I(CO)3Ru(μ-SeCH2Ph)2Ru(CO)3I] (8). Metallacycle 8
was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), dibenzyldiselenide (0.15 mmol), and iodine
(0.2 mmol), and the compound was obtained as a red solid. Yield: 57
1
mg, 66%. IR (CH2Cl2): ν(CO) 2107(m), 2053(s), 1994(m) cm−1. H
NMR (400 MHz, CDCl3, ppm): δ 7.34 (m, 5H, o-, m-, and p-H, ph),
ab
3.88 (s, 2H, benzyl H). UV−vis {(CH2Cl2)/λmax (nm)}: 249, 340.
Anal. Calcd for C20H14I2O6Ru2Se2: C, 24.91; H, 1.46. Found: C, 24.93;
H, 1.48.
Synthesis of [Br(CO)3Ru(μ-TePh)2Ru(CO)3Br] (9). Metallacycle 9
was synthesized by following the procedure adopted for 1, using
Ru3(CO)12 (0.1 mmol), diphenylditelluride (0.15 mmol), and
bromine (0.2 mmol), and the compound was obtained as a red
solid. Yield: 71 mg, 76.70%. IR (CH2Cl2): ν(CO) 2114(m), 2103(s),
2055(s), 2038(s), 1997(w) cm−1. 1H NMR (400 MHz, CDCl3, ppm):
δ 7.68 (dd, 2H, o-H ph), 7.38 (tt, 1H, p-H ph), 7.31 (tt, 2H, m-H ph).
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