N-Chloronitrenokomplexe des Wolframs: Synthesen und Kristallstrukturen von PPh3Me[Cl5W(NCl)] und (PPh4)3{[Cl5W(NCl)]2Cl} • CCl4 • 4CH3CN / N-Chloro-Nitrene Complexes of Tungsten: Syntheses and Crystal Structures of PPh3Me[Cl5W(NCl)] and (PPh4)3{[Cl5W(NCl)]2Cl} CCl4-4CH3CN

Abstract

Abstrct The N-chloro-nitrene complexes PPh3Me[Cl5W(NCl)] and (PPh4)3{ [Cl5W(NCl)]2Cl} • CCl4 • 4CH3CN were prepared by the reaction of [CI4W(NCl)]2 with [PPh3Me]Ci in CH2Cl2 and with [PPh4]Cl in CH3CN. respectively, followed by precipitation with CCl4. Both compounds form red, moisture-sensitive crystals, which were characterized by IR spectroscopy as well as by X-ray structure determinations. PPh3Me[CUW(NCl)]: space group P1̄, Z = 2, a = 862.7(3), b = 1108.4(2), c = 1411.0(5) pm. a = 71.74(3)°, β = 76.78(3)°, y = 77.55(2)° (at 18 °C); 2843 unique observed reflexions, R = 0.042. The compound consists of ions PPh3Me+ and [Cl5W(NCl)]-, in which the tungsten atom has a distorted octahedral environment of five chlorine atoms and the nitrogen atom of the N-chloro-nitrene ligand with bond distances WN = 169 pm and N-Cl = 160 pm. bond angle WNCl = 175°. (PPh4)3{[Cl5W(NCl)]2Cl} • CCl4• 4CH3CN: space group P4/n, Z = 2, a = 1298.2(8). c = 2720.4(7) pm (at 17 °C); (1979 unique observed reflexions. R = 0.096). The compound contains cations PPh4 + and anions {[CI5W(NCl)]2Cl}3-, in which two [Cl5W(NCl)]- ions are bridged by a chloride ion to form the linear unit [Cl5W≡N-Cl ··· Cl -Cl-N≡WCl5]3- with Cl ··· Cl-contactsof 288 and 278 pm