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 Scopus citations

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

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

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