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The solid-state molecular structure of W(NO)^sub 3^Cl^sub 3^ and the nature of its W-NO bonding1
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The solid-state molecular structure of W(NO)^sub 3^Cl^sub 3^ and the nature of its W-NO bonding1
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Journal Article
The solid-state molecular structure of W(NO)^sub 3^Cl^sub 3^ and the nature of its W-NO bonding1
2004
Overview
The monomeric trinitrosyl complex, W(NO)^sub 3^Cl^sub 3^, can be prepared by the treatment of WCl^sub 6^ in CH^sub 2^Cl^sub 2^ with NO gas, and its identity has been unambiguously confirmed by a single-crystal X-ray diffraction analysis. The complex crystallizes in the space group Pmw2^sub 1^ as a three-component twin (a = 10.4280(4) [Angstrom], b = 6.3289(2) [Angstrom], c = 5.6854(2) [Angstrom], Z = 2, R^sub 1^ = 0.065, wR^sub 2^ = 0.176). Its solid-state molecular structure consists of a tungsten centre bound to three chloride ligands and three linear nitrosyl ligands in a fac-octahedral stereochemistry. In addition, the structure contains a crystallographically imposed mirror plane. The two independent W-N linkages are 1.88(2) and 1.92(1) [Angstrom] long, while the two corresponding N-O bond lengths are 1.13(2) and 1.16(2) [Angstrom]. DFT calculations on fac-W(NO)^sub 3^Cl^sub 3^ at the B3LYP/LANL2DZ level of theory afford optimized intramolecular metrical parameters that match the X-ray crystallographically determined bond lengths and bond angles quite well. In addition, they provide a rationale for the nearly linear W-N-O linkages extant in the complex. Solutions of fac-W(NO)^sub 3^Cl^sub 3^ in CH^sub 2^Cl^sub 2^ lose ClNO under ambient conditions and deposit the well-known [W(NO)^sub 2^Cl^sub 2^]^sub n^ polymer, and this conversion is fully reversible. [PUBLICATION ABSTRACT] Key words: nitrosyl, tungsten, structure, bonding.
Publisher
Canadian Science Publishing NRC Research Press
Subject
