On the Preparation, Structure and Bonding of Rescl3
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Chem. Met. Alloys 8 (2015) 43-54 Ivan Franko National University of Lviv www.chemetal-journal.org On the preparation, structure and bonding of ReSCl 3 S.V. VOLKOV 1, V.V. SUBBOTIN 1, P.Yu. DEMCHENKO 2, R.E. GLADYSHEVSKII 2, O.G. YANKO 1*, L.B. KHARKOVA 1 1 V. Vernadsky Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, Palladin Ave. 32/34, UA-03680 Kyiv, Ukraine 2 Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya St. 6, UA-79005 Lviv, Ukraine * Corresponding author. E-mail: [email protected] Received May 25, 2015; accepted June 24, 2015; available on-line September 1, 2015 The reaction of Re 2O7 with a solution of S in S 2Cl 2 at 100°C produced rhenium sulfur trichloride, ReSCl 3. The compound was found to have a polymeric linear structure [{ReCl 2(µµµ-Cl)} 2(µµµ-S) 2]∞∞∞, which represents a new structure type (space group C2/ m, a = 11.4950(7), b = 6.5626(3), c = 5.9938(4) Å, β = 95.199(4)°, Z = 4). The structure is closely related to the NbCl 4-type and expands the series of similar one-dimensional chain structures. Distorted Re[Cl 4S2] octahedra share edges to form infinite straight chains along the [010] direction and the Re atoms are arranged in pairs with alternatively short (2.965 Å) and long (3.598 Å) Re–Re distances. Electronic structure calculations and chemical bonding analysis, using the electron density/electron-localizability indicator (ELI) approach, indicated overall metallic character and revealed a combination of covalent polar Re–Cl and Re–S bonds and weak Re–Re non-polar metallic bonds, yielding the +3.40 –1.20 –0.68 –0.84 ELI-based oxidation numbers (ELIBON) Re S [Cl1 ]2Cl2 . Rhenium sulfidochlorides / Crystal structure / One-dimensional chain structures / Density functional calculations / Electron localizability indicator / Chemical bonding Introduction By allowing ReS 2 or Re 2S7 and chlorine to react at different temperatures, ReSCl 2 and Re 2S3Cl 4 were Syntheses of rhenium chalcogenido-halides in systems formed [3,4] by breaking of Re–S bonds and containing rhenium, sulfur and chlorine have led to formation of Re–Cl bonds. Sulfur chlorides were the formation of 14 rhenium sulfidochlorides, which formed as by-products. Rhenium(VII) sulfide begins are simple, coordination or cluster compounds. Most to interact with chlorine at 120°C, whereas of them have been obtained by solid-state synthesis, rhenium(IV) sulfide does so at considerably higher and only for five of them a complete crystal structure temperatures (400-450°C). Chlorination of Re 2S3Cl 4 at determination has been performed ( Table 1). 400-450°C also yields ReSCl 2 [3] . For instance, sulfidochlorides of the composition A distinctive feature of the interaction of metallic ReSCl 2 [1,2] , ReSCl 4 [1] , ReS 3Cl ⋅S2Cl 2 [1] , and rhenium with its pentachloride and sulfur is the Re 2S3Cl 4 [1] have been obtained by the interaction of relatively low reaction rate, which is controlled by the cluster trirhenium nonachloride and rhenium diffusion in the solid state. Re 6S4Cl 10 and Re 6S5Cl 8, pentachloride with sulfur in a wide temperature range which belong to a series with the general formula and in a wide range of molar ratios of the constituents. Re 6S4+ qCl 10–2q (where q = 0-4), have been obtained by It can be pointed out as a general rule that an increase controlled heating of finely ground, blended and of the temperature (125-240°C) results in the pressed mixtures in evacuated silica tubes at substitution of an increasing number of sulfur atoms 450-825°C. The composition of the reaction products for chlorine. The ratio of the reagents does in general is mainly determined by the ratio of the constituents not affect the composition of the reaction product. [11] . The reaction of rhenium with sulfur and chlorine Unfortunately, it is not always possible to predict the at 1060-1100°C led to the formation of Re 6S8Cl 2, composition. Therefore, the ratio of the reagents was belonging to the same series [12] . Varying the ratio of generally chosen arbitrarily, using a large excess of the starting substances, other rhenium sulfidochlorides the reagent that can easily be removed after the of this series can probably be synthesized as well. This synthesis. means that syntheses of this kind are fully predictable Chem. Met. Alloys 8 (2015) 43 S.V. Volkov et al ., On the preparation, structure and bonding of ReSCl 3 Table 1 Preparation methods used for known rhenium sulfidochlorides. No. Compound Preparation method, conditions Reference 1 ReSCl 2 2ReCl 5 + 4S, 160-270°C [1] Re 3Cl 9 + S [2] Re 2S7 + Cl 2, 400-450°C [3] ReS 2 + Cl 2, 400-450°C [3,4] Re 2S3Cl 4 + Cl 2, 400-450°C [3] 2 ReSCl 3 ReCl 5 + Sb 2S3, in CS 2 at 20°C [5] ReCl 5 + S 2Cl 2, 140°C [6] 3 ReSCl 4 ReCl 5 + S, 125°C [1] Re 3Cl 9 + S 2Cl 2, DTA [1] 4 ReS 3Cl ⋅S2Cl 2 2ReCl 5 + 8S, 220°C [1] 2ReCl 5 + 9S, 240°C [1] ReCl 5 + 7S, 200°C [1] ReS 2 + S 2Cl 2, DTA [1] 5 Re 2S3Cl 4 2ReCl 5 + 4S, 125-160°C [1] 2ReCl 5 + 9S, 180°C [1] Re 2S7 + Cl 2/CO 2 (1:5), 120°C [3] 6 ReS 2Cl 3 ReCl 5 + S 2Cl 2, 300°C [6] 7 ReCl 5(SCl 2)4 ReCl 5 + SCl 2, 20-100°C [6] a 8 Re 2SCl 12 ReCl 5 + S 2Cl 2, 20°C [7] Re + SCl 2, 400°C [8] 9 Re 2S4Cl 7 ReCl 5 + S + S 2Cl 2, 20-100°C [7] ReCl 5 + S 2Cl 2, in CS 2 at 20°C [7] 10 Re 3S4Cl 8 Re 2S4Cl 7 + S 2Cl 2, 250°C [7] b 11 Re 3S7Cl 7 ReOCl 4 + S + S 2Cl 2, 200°C [9] Re 2O7 + S + S 2Cl 2, 200°C [7] ReCl 4 + S + S 2Cl 2, 130°C [10] c 12 Re 6S4Cl 10 ReCl 5 + Re + S, 450-825°C [11] d 13 Re 6S5Cl 8 ReCl 5 + Re + S, 450-825°C [11] e 14 Re 6S8Cl 2 Re + S + Cl 2, 1060-1100°C [12] Crystallographic data: a SCl 3[Re 2Cl 9]: monoclinic, P21/m, a = 8.341(4), b = 10.533(5), c = 8.661(4) Å, β = 91.90(4)°, Z = 2 [8]. b Re 3S7Cl 7: trigonal, P3, a = 8.999(3), c = 22.516(5) Å, Z = 4 [9] , and trigonal, P31 c, a = 8.9983(3), c = 22.493(2) Å, Z = 4 [10] . c Re 6S4Cl 10 : triclinic, P-1, a = 8.910(2), b = 12.441(2), c = 8.842(1) Å, α = 95.79(1), β = 97.61(1), γ = 83.68(1)°, Z = 2 [11]. d Re 6S5Cl 8: triclinic, P-1, a = 9.050(3), b = 13.045(4), c = 8.767(4) Å, α = 96.08(4), β = 116.08(3), γ = 80.50(3)°, Z = 2 [11]. e Re 6S8Cl 2: monoclinic, P21/n, a = 6.364(1), b = 11.304(2), c = 9.914(2) Å, β = 100.40(1)°, Z = 2 [12]. as to the end product. The compounds forming in the media. Liquid sulfur chlorides usually act as solvents above systems contain rhenium in the low oxidation and starting reagents at the same time. Rhenium state +3 and are hexanuclear cluster sulfidochlorides pentachloride gives the adduct ReCl 5⋅4SCl 2 in sulfur [Re 6(µ3-S) 8-q(µ3-Cl) q]Cl q+2 (where q = 0-4) [11,12] . dichloride at 20-100°C [6] , while in sulfur This explains their high thermal and chemical monochloride ReSCl 3 [6] , ReS 2Cl 3 [6] and Re 2SCl 12 stability. The main disadvantages of heterogeneous [7] are observed at different temperatures. According synthesis are the diffusion barriers, which limit the to the authors’ assumption, the first two compounds rate of the processes, and often the impossibility to are polymers. The last compound, which has also been obtain high-purity homogeneous products. obtained by the interaction of metallic rhenium with An advantage of the same methods is that the sulfur dichloride at 400°C [8] , is an ionic complex + – possibility to carry out the synthesis at ~1000°C (SCl 3) [Re 2Cl 9] . Re 3Cl 9 interacts with S 2Cl 2 to form allows obtaining cluster structures that do not form at ReSCl 4 [1] , while ReS 2 forms ReS 3Cl ⋅S2Cl 2 [1] . low temperatures. Solution of sulfur in S 2Cl 2 with ReCl 5 produces Non-aqueous solvents such as sulfur chlorides and Re 2S4Cl 7 [7] , while with rhenium(VI) oxychloride [9] , carbon disulfide have been used as reaction media for rhenium(VII) oxide [7] and rhenium(IV) chloride [8] , the synthesis of rhenium sulfidochlorides in liquid a trinuclear cluster Re 3S7Cl 7 of the structure 44 Chem. Met. Alloys 8 (2015) S.V. Volkov et al ., On the preparation, structure and bonding of ReSCl 3 + – [Re 3(µ3-S)( µ-S2)3Cl 6] Cl was observed. In carbon (1.1 g, 82 % yield) was obtained, which rapidly disulfide, ReSCl 3 [5] is formed from the starting decomposes in air. compound ReCl 5 in the presence of Sb 2S3, and Re 2S4Cl 7 [7] in the presence of S 2Cl 2, with subsequent Characterization transformation into the trinuclear complex Re 3S4Cl 8 Elemental analysis was performed on an ElvaX Light [7] at 250°C.