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Title: Lewis acid behavior of ReO{sub 2}F{sub 3}: Synthesis of (ReO{sub 2}F{sub 3}){sub {infinity}}, ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, Re{sub 3}O{sub 6}F{sub 10}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) and study by NMR spectroscopy, Raman spectroscopy, and density functional theory calculations; and X-ray structures of [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN

Abstract

The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solid state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4}more » units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.« less

Authors:
; ; ; ;  [1];  [2]
  1. McMaster Univ. Hamilton, Ontario (Canada). Dept. of Chemistry
  2. Pacific Northwest National Lab., Richland, WA (United States). William R. Wiley Environmental Molecular Sciences Lab.
Publication Date:
Sponsoring Org.:
Natural Sciences and Engineering Research Council of Canada, Ottawa, ON (Canada); Petroleum Research Fund (United States); National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
OSTI Identifier:
354360
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 38; Journal Issue: 10; Other Information: PBD: 17 May 1999
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; OXYFLUORIDES; RHENIUM COMPOUNDS; CHEMICAL PREPARATION; CRYSTAL STRUCTURE; LITHIUM COMPOUNDS; POTASSIUM COMPOUNDS; CESIUM COMPOUNDS

Citation Formats

Casteel, W.J. Jr., LeBlond, N., Lock, P.E., Mercier, H.P.A., Schrobilgen, G.J., and Dixon, D.A. Lewis acid behavior of ReO{sub 2}F{sub 3}: Synthesis of (ReO{sub 2}F{sub 3}){sub {infinity}}, ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, Re{sub 3}O{sub 6}F{sub 10}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) and study by NMR spectroscopy, Raman spectroscopy, and density functional theory calculations; and X-ray structures of [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN. United States: N. p., 1999. Web. doi:10.1021/ic980695t.
Casteel, W.J. Jr., LeBlond, N., Lock, P.E., Mercier, H.P.A., Schrobilgen, G.J., & Dixon, D.A. Lewis acid behavior of ReO{sub 2}F{sub 3}: Synthesis of (ReO{sub 2}F{sub 3}){sub {infinity}}, ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, Re{sub 3}O{sub 6}F{sub 10}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) and study by NMR spectroscopy, Raman spectroscopy, and density functional theory calculations; and X-ray structures of [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN. United States. doi:10.1021/ic980695t.
Casteel, W.J. Jr., LeBlond, N., Lock, P.E., Mercier, H.P.A., Schrobilgen, G.J., and Dixon, D.A. Mon . "Lewis acid behavior of ReO{sub 2}F{sub 3}: Synthesis of (ReO{sub 2}F{sub 3}){sub {infinity}}, ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, Re{sub 3}O{sub 6}F{sub 10}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) and study by NMR spectroscopy, Raman spectroscopy, and density functional theory calculations; and X-ray structures of [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN". United States. doi:10.1021/ic980695t.
@article{osti_354360,
title = {Lewis acid behavior of ReO{sub 2}F{sub 3}: Synthesis of (ReO{sub 2}F{sub 3}){sub {infinity}}, ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, Re{sub 3}O{sub 6}F{sub 10}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) and study by NMR spectroscopy, Raman spectroscopy, and density functional theory calculations; and X-ray structures of [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN},
author = {Casteel, W.J. Jr. and LeBlond, N. and Lock, P.E. and Mercier, H.P.A. and Schrobilgen, G.J. and Dixon, D.A.},
abstractNote = {The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solid state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.},
doi = {10.1021/ic980695t},
journal = {Inorganic Chemistry},
number = 10,
volume = 38,
place = {United States},
year = {Mon May 17 00:00:00 EDT 1999},
month = {Mon May 17 00:00:00 EDT 1999}
}