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 language | English (US) |
|---|---|
| Pages (from-to) | 485-490 |
| Number of pages | 6 |
| Journal | European Journal of Inorganic Chemistry |
| Issue number | 3 |
| State | Published - 2000 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - 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
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.
KW - Coordination modes
KW - Cyclophanes
KW - Macrocycles
KW - Sandwich complexes
KW - Solid- state structures
UR - http://www.scopus.com/inward/record.url?scp=0034048706&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034048706&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0034048706
SP - 485
EP - 490
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 3
ER -