SYNTHESIS AND STRUCTURE OF WNCL3 AND EVIDENCE FOR STRUCTURAL MODIFICATIONS WITH BOUND CHLOROCARBON SOLVENTS

A convenient synthesis of WNCl3 resulted from the reaction between WCl 6 and Me(3)SiN(3) in 1:1 molar ratio in refluxing 1,2-dichloroethane ( DCE) at 84 degrees C, The isolated material was shown by elemental ana lysis, IR, and NMR to be WNCl3.1.1DCE. Heating in vacuo at 160 degrees C was required to remove the DCE and give unsolvated [WNCl3](4). Crys tals of the latter were grown by sublimation in a sealed tube under a temperature gradient of 290/300 degrees C. WNCl3 is isostructural with MoNCl3; triclinic P1 $($) over bar$$, a = 7.752(2) Angstrom, b = 8.14 3(2) Angstrom, c = 9.114(2) Angstrom, alpha = 98.71(3)degrees, beta = 107.52(3)degrees, gamma = 110.40(3)degrees, Z = 4, R = 0.0431, R(W), = 0.0554. The structure is composed of [WNl(3)](4) molecules interconne cted through W-Cl-W bridge bonding. The tetramers consist of planar W4 N4 rings with alternating short and long W-N bonds, with average dista nces of 1.696(7) and 2.082(7) Angstrom, respectively, similar to sever al complexes [WNCl3.L](4) known previously.