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Title: Tetrakis(pyridine)tetrachloro(. mu. -chloro)(. mu. -hydrido)ditungsten (W-W) and its 4-ethylpyridine homologue. Compounds derived from a quadruply bonded dimer by ligand exchange and oxidative addition of hydrogen chloride

Abstract

Reaction of W{sub 2}(mhp){sub 4} (mhp = anion of 6-methyl-2-hydroxypyridine) with (CH{sub 3}){sub 3}SiCl and pyridine in the presence of methanol provides the light brown compound W{sub 2}HCl{sub 5}(NC{sub 5}H{sub 5}){sub 4}. The 4-ethylpyridine adduct W{sub 2}HCl{sub 5}(NC{sub 5}H{sub 4}C{sub 2}H{sub 5}){sub 4} is obtained by ligand exchange at 100{degree}C. Brown crystals of the latter are monoclinic, space group C2/c, with a = 11.883 (3) {angstrom}, b = 13.213 (3) {angstrom}, c = 21.727 (4) {angstrom}, {beta} = 96.39 (3){degree}, and Z = 4. Structure refinement revealed an edge-shared bioctahedral arrangement with one H atom and one Cl atom in bridging positions between the metal atoms. The Cl atoms all occupy positions in the equatorial plane, and the 4-ethylpyridine ligands occupy the axial positions of the dimer. The short W-W distance, 2.516 (2) {angstrom}, is consistent with a W-W multiple bond. Comparison of the infrared spectra of the hydride and deuteride derivatives confirms the presence of a bridging H atom and indicates an isostructural arrangement for the pyridine and 4-ethylpyridine derivatives, as do electronic reflectance spectra. 33 refs., 4 figs., 4 tabs.

Authors:
;  [1]
  1. Iowa State Univ., Ames (USA)
Publication Date:
OSTI Identifier:
5052959
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (USA)
Additional Journal Information:
Journal Volume: 28:13; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHLORINE COMPOUNDS; CHEMICAL PREPARATION; HYDROXY COMPOUNDS; PYRIDINE; TUNGSTEN COMPLEXES; CRYSTAL STRUCTURE; EXPERIMENTAL DATA; AZINES; COMPLEXES; DATA; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PYRIDINES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Carlin, R T, and McCarley, R E. Tetrakis(pyridine)tetrachloro(. mu. -chloro)(. mu. -hydrido)ditungsten (W-W) and its 4-ethylpyridine homologue. Compounds derived from a quadruply bonded dimer by ligand exchange and oxidative addition of hydrogen chloride. United States: N. p., 1989. Web. doi:10.1021/ic00312a020.
Carlin, R T, & McCarley, R E. Tetrakis(pyridine)tetrachloro(. mu. -chloro)(. mu. -hydrido)ditungsten (W-W) and its 4-ethylpyridine homologue. Compounds derived from a quadruply bonded dimer by ligand exchange and oxidative addition of hydrogen chloride. United States. https://doi.org/10.1021/ic00312a020
Carlin, R T, and McCarley, R E. 1989. "Tetrakis(pyridine)tetrachloro(. mu. -chloro)(. mu. -hydrido)ditungsten (W-W) and its 4-ethylpyridine homologue. Compounds derived from a quadruply bonded dimer by ligand exchange and oxidative addition of hydrogen chloride". United States. https://doi.org/10.1021/ic00312a020.
@article{osti_5052959,
title = {Tetrakis(pyridine)tetrachloro(. mu. -chloro)(. mu. -hydrido)ditungsten (W-W) and its 4-ethylpyridine homologue. Compounds derived from a quadruply bonded dimer by ligand exchange and oxidative addition of hydrogen chloride},
author = {Carlin, R T and McCarley, R E},
abstractNote = {Reaction of W{sub 2}(mhp){sub 4} (mhp = anion of 6-methyl-2-hydroxypyridine) with (CH{sub 3}){sub 3}SiCl and pyridine in the presence of methanol provides the light brown compound W{sub 2}HCl{sub 5}(NC{sub 5}H{sub 5}){sub 4}. The 4-ethylpyridine adduct W{sub 2}HCl{sub 5}(NC{sub 5}H{sub 4}C{sub 2}H{sub 5}){sub 4} is obtained by ligand exchange at 100{degree}C. Brown crystals of the latter are monoclinic, space group C2/c, with a = 11.883 (3) {angstrom}, b = 13.213 (3) {angstrom}, c = 21.727 (4) {angstrom}, {beta} = 96.39 (3){degree}, and Z = 4. Structure refinement revealed an edge-shared bioctahedral arrangement with one H atom and one Cl atom in bridging positions between the metal atoms. The Cl atoms all occupy positions in the equatorial plane, and the 4-ethylpyridine ligands occupy the axial positions of the dimer. The short W-W distance, 2.516 (2) {angstrom}, is consistent with a W-W multiple bond. Comparison of the infrared spectra of the hydride and deuteride derivatives confirms the presence of a bridging H atom and indicates an isostructural arrangement for the pyridine and 4-ethylpyridine derivatives, as do electronic reflectance spectra. 33 refs., 4 figs., 4 tabs.},
doi = {10.1021/ic00312a020},
url = {https://www.osti.gov/biblio/5052959}, journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 28:13,
place = {United States},
year = {Wed Jun 28 00:00:00 EDT 1989},
month = {Wed Jun 28 00:00:00 EDT 1989}
}