N-Chlornitrenokomplexe des Wolframs: WCl4 (NCl) und [CH3CN-WCl4 (NCl)] / N-Chloro-Nitrene Complexes of Tungsten:WCl4 (NCl) and [CH3CN-WCl4 (NCl)]

Author:

Görge Astrid1,Dehnicke Kurt1,Fenske Dieter2

Affiliation:

1. Fachbereich Chemie der Universität Marburg, Hans-Meerwein-Straße. D-3550 Marburg/Lahn

2. Institut für Anorganische Chemie der Universität Frankfurt, Niederurseier Hang, D-6000 Frankfurt/Main

Abstract

WCl4(NCl) has been prepared as a red-brown crystal powder by the reaction of tungsten hexacarbonyl with excess nitrogen trichloride in boiling CCl4. The complex is associated via chloro bridges, forming dimeric units, according to the IR spectrum. Thermal decomposition at 200 °C leads to tungsten nitride trichloride, WNCl3,. With acetonitrile, WCl4(NCl) reacts with formation of the monomeric complex [CH,CN-WCl4(NCl)], which was characterized by its IR spectrum as well as by an X-ray structure determination. Crystal data: space group P21/m, Z = 2 (1387 independent observed reflexions, R = 0.07). Lattice dimensions at 20 °C: a = 590.4(3), b = 729.0(3), c = 1124.6(4) pm, β = 100.63(2)°. The complex forms monomeric molecules, in which the tungsten atom has a distorted octahedral environment of four chlorine atoms in equatorial positions, and the acetonitrile molecule in trans-position to the group. Bond lengths WN = 172 and NCI = 161 pm; bond angle WNCl = 175.5°.

Publisher

Walter de Gruyter GmbH

Subject

General Chemistry

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