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Title: New pathways to tungsten and molybdenum oxides, nitrides and azides

Abstract

[WNCl[sub 3]][sub 4] was prepared and characterized structurally by X-ray diffraction. [WNCl[sub 3]][sub 4] crystallizes in space group P[bar 1] as planar 8-membered W-N rings interconnected through chloride bridges. The inter-tetramer linkage is weak and broken easily to accommodate basic ligands in the site trans to the W-N triple bond. Reactivity of WNCl[sub 3], with nitriding agents, such as ammonia, trimethylsilylazide and lithium nitride, has been investigated, which resulted in preparation of new tungsten azido and nitrido compounds. Second, the reactivity of the metal dimers MO[sub 2](O[sub 2]CCH[sub 3])[sub 4] and MO[sub 2]Cl[sub 4]py[sub 4] with trimethylsilylazide has been explored, and the reactions in pyridine were found to yield a material corresponding to the formulation, MoN(N[sub 3])py. Thermolytic decomposition of this azide at 280[degree]C was performed under argon, dynamic vacuum or ammonia. Thermal decomposition in ammonia produces a molybdenum nitride relatively free of carbon with a Mo:N ratio of 1:1.8. WNCl[sub 3] was converted into a hexagonal ammonium tungsten bronze, (NH[sub 4])[sub 0.28]WO[sub 3-y](NH)[sub y]. This synthesis increased the probability of isoelectronic imido substitution for oxide in the bronze framework. Rietveld refinements of neutron powder data indicated strongly that nitrogen, in the form of imide, does not substitute for oxygen.more » A model for ammonium cation motion in the hexagonal channels of the bronze was developed. Electrical resistivity measurements on a pressed pellet of this hexagonal bronze show a temperature dependence like that of a low-band gap semiconductor, in contrast to conventionally prepared metallic hexagonal bronze phases.« less

Authors:
Publication Date:
Research Org.:
Ames Lab., IA (United States)
Sponsoring Org.:
USDOE; USDOE, Washington, DC (United States)
OSTI Identifier:
7165915
Report Number(s):
IS-T-1608
ON: DE93003051
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Technical Report
Resource Relation:
Other Information: Thesis (Ph.D.)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLYBDENUM NITRIDES; SYNTHESIS; TUNGSTATES; TUNGSTEN COMPLEXES; TUNGSTEN NITRIDES; AMIDES; AMMONIUM COMPOUNDS; AZIDES; ELECTRIC CONDUCTIVITY; HEXAGONAL LATTICES; INFRARED SPECTRA; MOLYBDENUM COMPLEXES; NITROGEN COMPOUNDS; PYRIDINE; PYROLYSIS; TUNGSTEN CHLORIDES; X-RAY DIFFRACTION; AZINES; CHEMICAL REACTIONS; CHLORIDES; CHLORINE COMPOUNDS; COHERENT SCATTERING; COMPLEXES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DECOMPOSITION; DIFFRACTION; ELECTRICAL PROPERTIES; HALIDES; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; MOLYBDENUM COMPOUNDS; NITRIDES; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHYSICAL PROPERTIES; PNICTIDES; PYRIDINES; REFRACTORY METAL COMPOUNDS; SCATTERING; SPECTRA; THERMOCHEMICAL PROCESSES; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS; TUNGSTEN COMPOUNDS; 360201* - Ceramics, Cermets, & Refractories- Preparation & Fabrication; 400201 - Chemical & Physicochemical Properties

Citation Formats

Close, M R. New pathways to tungsten and molybdenum oxides, nitrides and azides. United States: N. p., 1992. Web.
Close, M R. New pathways to tungsten and molybdenum oxides, nitrides and azides. United States.
Close, M R. Wed . "New pathways to tungsten and molybdenum oxides, nitrides and azides". United States.
@article{osti_7165915,
title = {New pathways to tungsten and molybdenum oxides, nitrides and azides},
author = {Close, M R},
abstractNote = {[WNCl[sub 3]][sub 4] was prepared and characterized structurally by X-ray diffraction. [WNCl[sub 3]][sub 4] crystallizes in space group P[bar 1] as planar 8-membered W-N rings interconnected through chloride bridges. The inter-tetramer linkage is weak and broken easily to accommodate basic ligands in the site trans to the W-N triple bond. Reactivity of WNCl[sub 3], with nitriding agents, such as ammonia, trimethylsilylazide and lithium nitride, has been investigated, which resulted in preparation of new tungsten azido and nitrido compounds. Second, the reactivity of the metal dimers MO[sub 2](O[sub 2]CCH[sub 3])[sub 4] and MO[sub 2]Cl[sub 4]py[sub 4] with trimethylsilylazide has been explored, and the reactions in pyridine were found to yield a material corresponding to the formulation, MoN(N[sub 3])py. Thermolytic decomposition of this azide at 280[degree]C was performed under argon, dynamic vacuum or ammonia. Thermal decomposition in ammonia produces a molybdenum nitride relatively free of carbon with a Mo:N ratio of 1:1.8. WNCl[sub 3] was converted into a hexagonal ammonium tungsten bronze, (NH[sub 4])[sub 0.28]WO[sub 3-y](NH)[sub y]. This synthesis increased the probability of isoelectronic imido substitution for oxide in the bronze framework. Rietveld refinements of neutron powder data indicated strongly that nitrogen, in the form of imide, does not substitute for oxygen. A model for ammonium cation motion in the hexagonal channels of the bronze was developed. Electrical resistivity measurements on a pressed pellet of this hexagonal bronze show a temperature dependence like that of a low-band gap semiconductor, in contrast to conventionally prepared metallic hexagonal bronze phases.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1992},
month = {10}
}

Technical Report:
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