Reversible extrusion and uptake of HCl molecules by crystalline solids involving coordination bond cleavage and formation

G.M. Espallargas, L. Brammer, J. van de Streek, K. Shankland, A.J. Florence, H. Adams

Research output: Contribution to journalArticle

93 Citations (Scopus)

Abstract

Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.
LanguageEnglish
Pages9584-85
Number of pages9499
JournalJournal of American Chemical Society
Volume128
Issue number30
DOIs
Publication statusPublished - 2006

Fingerprint

Extrusion
Salts
Crystalline materials
Powder Diffraction
Molecules
Least-Squares Analysis
X-Ray Diffraction
Rietveld refinement
Metals
Air
X ray powder diffraction
Crystal structure
Vapors
Geometry
cupric chloride

Keywords

  • applied physiology
  • pharmacology
  • chemistry
  • bond cleavage
  • HCl molecules

Cite this

Espallargas, G.M. ; Brammer, L. ; van de Streek, J. ; Shankland, K. ; Florence, A.J. ; Adams, H. / Reversible extrusion and uptake of HCl molecules by crystalline solids involving coordination bond cleavage and formation. In: Journal of American Chemical Society. 2006 ; Vol. 128, No. 30. pp. 9584-85.
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abstract = "Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.",
keywords = "applied physiology, pharmacology, chemistry, bond cleavage, HCl molecules",
author = "G.M. Espallargas and L. Brammer and {van de Streek}, J. and K. Shankland and A.J. Florence and H. Adams",
year = "2006",
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Reversible extrusion and uptake of HCl molecules by crystalline solids involving coordination bond cleavage and formation. / Espallargas, G.M.; Brammer, L.; van de Streek, J.; Shankland, K.; Florence, A.J.; Adams, H.

In: Journal of American Chemical Society, Vol. 128, No. 30, 2006, p. 9584-85.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reversible extrusion and uptake of HCl molecules by crystalline solids involving coordination bond cleavage and formation

AU - Espallargas, G.M.

AU - Brammer, L.

AU - van de Streek, J.

AU - Shankland, K.

AU - Florence, A.J.

AU - Adams, H.

PY - 2006

Y1 - 2006

N2 - Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.

AB - Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.

KW - applied physiology

KW - pharmacology

KW - chemistry

KW - bond cleavage

KW - HCl molecules

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JO - Journal of the American Chemical Society

T2 - Journal of the American Chemical Society

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SN - 0002-7863

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