One-Pot Synthesis of Ruthenium Metallacycles via Oxidative Addition

Nov 27, 2013 - Department of Chemistry, Pondicherry University, Puducherry, 605014, India. ‡. National Single Crystal X-ray Diffraction Facility, In...
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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.

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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(μEPh)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.

with addition across the Ru−Ru bond afforded the chalcogenide-bridged dinuclear ruthenium metallacycles 1− 10. When ruthenium carbonyl was treated with diaryldichalcogenide, 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 supports 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. 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

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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 diaryldichalcogen 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 © 2013 American Chemical Society

Received: July 13, 2013 Published: November 27, 2013 7292

dx.doi.org/10.1021/om400686q | Organometallics 2013, 32, 7292−7296

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Scheme 1. Synthesis of Chalcogen-Bridged Dinuclear Ruthenium Metallacycles, [X(CO)3Ru(μ-ER)2Ru(CO)3X] (1−10)

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(μER)2Ru(CO)3X] 1, 4−7, 9, and 10 were determined by singlecrystal 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 group P1̅ (Table S1). A representative ORTEP diagram of 10 is shown in Figure 1. The central core of the metallacycles

room temperature, and the crystals were found to be air, light, and moisture stable. 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 Tebridged 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 Table 1. Comparison of IR Stretching Frequencies of Terminal CO Groups ν(CO) (cm−1)

compound 1 5 6 9 10

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)

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 iodinesubstituted ones, indicating that iodine favors Ru−CO backbonding more than bromine (Table 1, comparison of 5 and 6; 9 and 10). 1 H and 13C NMR spectra of metallacycles supported the formation of a single product in all reactions. 1H NMR spectra 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(μSPh)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(μSePh)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

Figure 1. ORTEP view of metallacycle [I(CO)3Ru(μ-TePh)2Ru(CO)3I] (10). Thermal ellipsoids are drawn at 40% probability.

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 7293

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Organometallics 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(μSePh)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

1 5 6 9 10

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)

torsional angle

Ru···Ru distance

16.64 10.91 9.53 11.40 10.54

3.646 3.795 3.811 4.032 4.040

CONCLUSION

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EXPERIMENTAL SECTION

We have demonstrated the successful synthesis of ruthenium(II)-based dinuclear metallacycles with bridging chalcogencontaining 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.

Table 2. Comparison of Torsional Angles (deg) and M···M Distances (Å) compound

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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 diaryldichalcogen 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 4000 spectrophotometer. 1H and 13C NMR spectra were recorded on a Avans Bruker 400 MHz spectrometer. Elemental analyses were performed in an Elementar Vario ELIII elemental analyzer. 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 lowtemperature 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 SHELXL97 refining on F2.19−21 The positions on all the atoms were obtained by direct methods. All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were placed in geometrically constrained positions and refined with isotropic temperature factors, generally 1.2Ueq of their parent atoms. 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): ν(CO) 2125(s), 2118(s), 2071(s), 2046(s), 2026(sh) cm−1. 1H 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, ph), 128.5 (p-C, ph). UV−vis {(CH2Cl2)/λmaxab (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:

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. 7294

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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, oand 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. 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-, m-, and p-H, ph), 3.08 (s, 2H, benzyl H). UV−vis {(CH2Cl2)/λmaxab (nm)}: 251. Anal. Calcd for C20H14Br2O6Ru2S2: C, 27.60; H, 1.60. Found: C, 27.62; H, 1.65. 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-, m-, and p-H, ph), 4.09 (m, 2H, benzyl H). UV−vis {(CH2Cl2)/λmaxab (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, oH, 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), 127.6 (p-C, ph), 127.0 (i-C, ph). UV−vis {(CH2Cl2)/λmaxab (nm)}: 257, 270. Anal. Calcd for C18H10Br2O6Ru2Se2: C, 25.67; H, 1.20. Found: C, 25.64; H, 1.18. 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, oH, 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), 129.3 (p-C, ph), 128.5 (i-C, ph). UV−vis {(CH2Cl2)/λmaxab (nm)}: 253, 345. Anal. Calcd for C18H10I2O6Ru2Se2: C, 23.09; H, 1.08. Found: C, 23.06; H, 1.08. 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-, m-, and p-H, ph), 3.91 (s, 2H, benzyl H). UV−vis {(CH2Cl2)/λmaxab (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 mg, 66%. IR (CH2Cl2): ν(CO) 2107(m), 2053(s), 1994(m) cm−1. 1H NMR (400 MHz, CDCl3, ppm): δ 7.34 (m, 5H, o-, m-, and p-H, ph), 3.88 (s, 2H, benzyl H). UV−vis {(CH2Cl2)/λmaxab (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).

C 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 {(CH2Cl2)/λmaxab (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, oH, 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 (m-C, ph), 128.1 (p-C, ph), 109.5 (i-C, ph). UV−vis {(CH2Cl2)/λmaxab (nm)}: 259, 305. Anal. Calcd for C18H10I2O6Ru2Te2: C, 20.92; H, 0.98. Found: C, 20.92; H, 1.01. 13

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ASSOCIATED CONTENT

S Supporting Information *

1

H 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.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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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.

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REFERENCES

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Organometallics

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dx.doi.org/10.1021/om400686q | Organometallics 2013, 32, 7292−7296