On the nature of arene η6 interactions in the solid state and the use of cylindrophanes as ligands for sandwich complexation of metals with longer- range interactions with the benzene ring

Mark Mascal, Jean Luc Kerdelhué, Alexander J. Blake, Paul A. Cooke, Roger J. Mortimer, Simon J. Teat

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

A novel mode of containment for metal ions which participate in longer- range interactions with aryl rings (≥ 2.5 Å) is demonstrated in the preorganized cylindrical host 1. Three equatorial sulfur atoms in 1 hold metals in a trigonal planar ligand field between two apical benzene centroids at an M-Ar distance of about 3 Å. Evidence of an interaction between the π electrons and the metals is gained by 1H NMR spectroscopy of the complexes, and support for the general description of metal-arene contacts in the 2.5- 3.5 Å range as 'bonds' is derived from a statistical study of η6- coordination in the solid state. Crystal structures of [Ag(1)]BF4 and [Cu(1)]BF4 confirm the first examples of arene Ag(I) and Cu(I) sandwich complexation and indeed the only structurally characterized Cu(I)-aryl centroid interaction. The two isomeric tris-sulfoxides derived from 1 show less tendency to interact with metals ions.

Original languageEnglish (US)
Pages (from-to)485-490
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Issue number3
StatePublished - 2000
Externally publishedYes

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Benzene
Complexation
Metals
Ligands
Metal ions
Sulfoxides
Sulfur
Nuclear magnetic resonance spectroscopy
Crystal structure
Atoms
Electrons

Keywords

  • Coordination modes
  • Cyclophanes
  • Macrocycles
  • Sandwich complexes
  • Solid- state structures

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

On the nature of arene η6 interactions in the solid state and the use of cylindrophanes as ligands for sandwich complexation of metals with longer- range interactions with the benzene ring. / Mascal, Mark; Kerdelhué, Jean Luc; Blake, Alexander J.; Cooke, Paul A.; Mortimer, Roger J.; Teat, Simon J.

In: European Journal of Inorganic Chemistry, No. 3, 2000, p. 485-490.

Research output: Contribution to journalArticle

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abstract = "A novel mode of containment for metal ions which participate in longer- range interactions with aryl rings (≥ 2.5 {\AA}) is demonstrated in the preorganized cylindrical host 1. Three equatorial sulfur atoms in 1 hold metals in a trigonal planar ligand field between two apical benzene centroids at an M-Ar distance of about 3 {\AA}. Evidence of an interaction between the π electrons and the metals is gained by 1H NMR spectroscopy of the complexes, and support for the general description of metal-arene contacts in the 2.5- 3.5 {\AA} range as 'bonds' is derived from a statistical study of η6- coordination in the solid state. Crystal structures of [Ag(1)]BF4 and [Cu(1)]BF4 confirm the first examples of arene Ag(I) and Cu(I) sandwich complexation and indeed the only structurally characterized Cu(I)-aryl centroid interaction. The two isomeric tris-sulfoxides derived from 1 show less tendency to interact with metals ions.",
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AU - Mascal, Mark

AU - Kerdelhué, Jean Luc

AU - Blake, Alexander J.

AU - Cooke, Paul A.

AU - Mortimer, Roger J.

AU - Teat, Simon J.

PY - 2000

Y1 - 2000

N2 - A novel mode of containment for metal ions which participate in longer- range interactions with aryl rings (≥ 2.5 Å) is demonstrated in the preorganized cylindrical host 1. Three equatorial sulfur atoms in 1 hold metals in a trigonal planar ligand field between two apical benzene centroids at an M-Ar distance of about 3 Å. Evidence of an interaction between the π electrons and the metals is gained by 1H NMR spectroscopy of the complexes, and support for the general description of metal-arene contacts in the 2.5- 3.5 Å range as 'bonds' is derived from a statistical study of η6- coordination in the solid state. Crystal structures of [Ag(1)]BF4 and [Cu(1)]BF4 confirm the first examples of arene Ag(I) and Cu(I) sandwich complexation and indeed the only structurally characterized Cu(I)-aryl centroid interaction. The two isomeric tris-sulfoxides derived from 1 show less tendency to interact with metals ions.

AB - A novel mode of containment for metal ions which participate in longer- range interactions with aryl rings (≥ 2.5 Å) is demonstrated in the preorganized cylindrical host 1. Three equatorial sulfur atoms in 1 hold metals in a trigonal planar ligand field between two apical benzene centroids at an M-Ar distance of about 3 Å. Evidence of an interaction between the π electrons and the metals is gained by 1H NMR spectroscopy of the complexes, and support for the general description of metal-arene contacts in the 2.5- 3.5 Å range as 'bonds' is derived from a statistical study of η6- coordination in the solid state. Crystal structures of [Ag(1)]BF4 and [Cu(1)]BF4 confirm the first examples of arene Ag(I) and Cu(I) sandwich complexation and indeed the only structurally characterized Cu(I)-aryl centroid interaction. The two isomeric tris-sulfoxides derived from 1 show less tendency to interact with metals ions.

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KW - Sandwich complexes

KW - Solid- state structures

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