Thionitrosylkomplexe des Rutheniums. Die Kristallstruktur von (PPh₄)₂[{RuBr₄(NS)}₂(μ‐N₂S₂)]

Abstract

Rutheniumtrichlorid reagiert mit Trithiazylchlorid in Thionylchlorid unter Bildung von cis‐RuCl4(NS)2. Mit Triphenylmethylphosphoniumchlorid entsteht hieraus der Chlorokomplex [RuCl4(NS)2Cl]⊖, in dem das Chloridion chelatartig von den S‐Atomen der Thionitrosylgruppen gebunden ist. Mit Tetraphenylphosphoniumbromid reagiert RuCl4(NS)2 unter Redox‐Reaktion zu (PPh4)2[{RuCl4(NS)}2(μ‐N2S2)], welches mit Trimethylsilylbromid in die Titelverbindung umgewandelt werden kann. Die IR‐Spektren werden mitgeteilt. (PPh4)2[{RuBr4(NS)}2(μ‐N2S2)] · 4 CH2X2 (X  Cl, Br) haben wir durch eine röntgenographische Strukturbestimmung charakterisiert (1534 beobachtete, unabhängige Reflexe, R = 8,5%). Es kristallisiert monoklin in der Raumgruppe P21/n mit zwei Formeleinheiten pro Elementarzelle. Die Gitterabmessungen sind a = 1680,7, b = 1287,0, c = 1706,1 pm und β = 99,97°. Die Verbindung besteht aus Tetraphenylphosphoniumkationen, CH2Br2 und CH2Cl2‐Molekülen (statistisch) und zentrosymmetrischen Anionen [{RuBr4(NS)}2(μ‐N2S2)]2⊖, in denen die Rutheniumatome über die N‐Atome eines ebenen N2S2‐Ringes verknüpft sind. In trans‐Position hierzu ist je ein Thionitrosylligand in gestreckter Anordnung RuNS koordiniert mit Abständen RuN von 169 pm und NS von 151 pm. Je vier terminale Bromatome ergänzen die verzerrt oktaedrische Umgebung an den Rutheniumatomen. Die coplanar zu dem verknüpfenden N2S2‐Ring angeordneten Bromatome bilden kurze S…︁Br‐Kontakte von im Mittel 317 pm aus.

Linear and Bent Oxo-Bridged Dimers of Ruthenium Pyrazole Nitrosyls

“…[7] Although this solid can be isolated as a trihydrate, it is frequently used directly for reactions with excess ligands L (L ϭ tertiary phosphanes and arsanes, thioethers, or selenyl ethers) [8Ϫ10] to give the diamagnetic complexes [RuCl 3 (NO)L 2 ] [Equation (1)]. [12] When anhydrous [RuCl 3 (NO)] is prepared in this manner, and then treated with excess 3,5-dimethylpyrazole in toluene at reflux [Equation (3)], the major product is mer-[RuCl 3 (NO)(dmpH) 2 ] (1), which is isolated in 87% yield after chromatography on silica. With amines and nitrogen bases this strategy has considerably less general utility; for example, although pyridine, acetonitrile, 2,2Јbipyridine, and 1,10phenanthroline add to [RuCl 3 (NO)] to give six-coordinate products, the reaction with ammonia, 3,5-dimethylpyrazole or {[tris (3,5-dimethylpyrazolyl)borate] Ϫ ϭ DMTPZ} under the conditions in Equation 1 leads to mixtures of products and low general yields of the desired product.…”

Crystal engineering strategies towards halogen-bonded metal–organic multi-component solids: salts, cocrystals and salt cocrystals

“…137 Unlike strategy 3a, strategy 3c has rarely been employed for a deliberate preparation of halogen-bonded materials to date, although numerous structures with this motif have been serendipitously obtained. [138][139][140][141][142][143][144] Rosokha, Kochi and coworkers have systematically studied bromine-containing donors, primarily tetrabromomethane, in salt cocrystals with a variety of (pseudo)halogenometallate anions (CuBr 2 − , ZnBr 4 2 , CoBr 4 2− , CdBr 4 2− , Pt 2 Br 6 2− and Zn(NCS) 4 2− ) as potential halogen bond acceptors and tetraalkylammonium cations as counterions not participating in halogen bonding (Fig. 19).…”

A four-coordinate thionitrosyl complex of vanadium

“…Consequently, reports of structurally characterized early transition metal thionitrosyl complexes are rare compared to thionitrosyl complexes featuring 4d and 5d late transition metals. 2,[9][10][11][12][13][14][15][16][17] We sought to isolate such species directly from a vanadium nitride and elemental sulfur and chose the vanadium nitride [(nacnac)VRN(OAr)] 18 (nacnac À = [ArNC(CH 3 )] 2 CH, Ar = 2,6-i Pr 2 C 6 H 3 ), since the metal is in a lowcoordinate environment, and the nitride ligand that is formally in a V (V) RN (3À) should be charge-polarized enough to act as a strong nucleophile attacking sulfur. In this work we describe the first vanadium thionitrosyl, which is characterized by a wide array of spectroscopic methods (including the 15 N enriched isotopologue), and single crystal X-ray diffraction studies.…”