Thiohalogeno‐Verbindungen von Niob und Tantal: NbSCl₃, TaSCl₃, [NbSCl₅]²⁻, [TaSCl₅]²⁻, [NbSBr₄]⁻ Die Kristallstrukturen von (PPh₄)₂[NbSCl₅] · 2 CH₂Cl₂ und NEt₄[NbCl₆]

Abstract

NbSCl3 kann aus einer Suspension von NbCl5 in CCl4 bzw. CH2Cl2 durch Reaktion mit H2S oder Bistrimethylsilylsulfid erhalten werden; im letzteren Fall enthält das Produkt noch Reste von Trimethylsilylgruppen. Dies gilt auch für TaSCl3, NbSBr3 und TaSBr3, die analog aus den Metallpentahalogeniden und S(SiMe3)2 entstehen. NEt4[NbSCl4] ist zusammen mit NEt4[NbCl6] aus NbCl5 und NEt4SH zugänglich. PPh4[NbCl6] reagiert mit S(SiMe3)2 in Dichlormethan zu (PPh4)2[NbSCl5] · 2 CH2Cl2, während aus PPh4[NbBr6] unter den gleichen Bedingungen PPh4[NbSBr4] entsteht. (PPh4)2[TaSCl5] · 2 CH2Cl2 wurde aus TaSCl3 und PPh4Cl in CH2Cl2 erhalten. Nach der röntgenographischen Kristallstrukturbestimmung kristallisiert (PPh4)2[NbSCl5] · 2 CH2Cl2 im β‐(AsPh4)[UCl6] · 2 CH2Cl2‐Typ mit fehlgeordneten, oktaedrischen Anionen. Kristalldaten: a = 1 021,7, b = 1 120,4, c = 1 243,3 pm, α = 70,77, β = 80,24, γ = 80,54°, Raumgruppe P1, Z = 2; 2 462 unabhängige beobachtete Reflexe, R = 3,6%. NEt4[NbCl6] kristallisiert isotyp zu NEt4[WCl6]: a = 723,5, b = 1 018,0, c = 1 174,6 pm, β = 100,07°, Raumgruppe P21/n, Z = 2; 1 875 Reflexe, R = 7,5%.

Coordination complexes and applications of transition metal sulfide and selenide halides

“…The NbEX3 (E = S, Se; X = Cl, Br) were made from NbX5 and the appropriate Sb2E3, with reaction in CS2 or CH2Cl2 giving a purer product than heating in sealed tubes [6,22,23]. More recently, reaction of NbX5 with E(SiMe3)2 has become favoured [24,25]. Spectroscopically identical products often exhibit a range of colours in different batches, for example, NbSCl3 has been variously described as golden yellow through to dark green.…”

“…The square pyramidal [NbSCl4]is made by reaction of NbSCl3 with the [Ph4P]Cl in CH2Cl2 [30], and this anion was also formed by photochemical irradiation of the reaction mixture of NbCl5 and tetramethylthiourea [31]. The [PPh4][NbSBr4] is formed from reaction of [PPh4][NbBr6] and S(SiMe3)2 [24], but the same reaction with [PPh4][NbCl6] produced the six-coordinate dianion in [PPh4]2[NbSCl5] [24]. The latter anion was also identified in the complex [Nb(S2CNEt2)4]2[NbSCl5],…”

“…TaSCl5] 2has been obtained as [PPh4] +[24] and Cs +[57] salts; the latter has the K2[PtCl6] structure.The anion is also present in the compound [Cp8Ta6S10][TaSCl5][58]. Unusual anions containing a coordinated dioxane ligand, [TaSCl4(dioxane)]and [(TaSCl4)2(µ-dioxane)] 2--(Fig.10) were obtained from reaction of TaCl5, Na2S4 and 15-crown-5 in CH2Cl2, with the dioxane derived from degradation of the crown ether[55].…”

One-Dimensional Molybdenum Thiochlorides and Their Use in High Surface Area MoSxChalcogels

“…Transition-metal thiohalides have been known for more than a century, and yet this class of compounds remains an insufficiently characterized group, as evidenced by the long known but inadequately characterized thiohalides, such as MSX 3 , (M = Nb, Mo, Ta, W; X = Cl, Br), − ReSCl 3 , , MSCl 2 (M = Ti, Mn, Nb, Mo, , W, Re , ), MS 2 Cl 2 (M = Mo, , W, , Re), and MSCl (M = Ti, V, Mo). Atherton et al., in 1979, summarized the synthesis and sparsely known chemistry of transition-metal chalcohalogenides .…”