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Tris(alkyne) and Bis(alkyne) Complexes of Coinage Metals: Synthesis and Characterization of (cyclooctyne)3M+ (M = Cu, Ag) and (cyclooctyne)2Au+ and Coinage Metal (M = Cu, Ag, Au) Family Group Trends

Authors :
Muhammed Yousufuddin
Gernot Frenking
H. V. Rasika Dias
Animesh Das
Mehmet Ali Celik
Chandrakanta Dash
Source :
Organometallics. 32:3135-3144
Publication Year :
2013
Publisher :
American Chemical Society (ACS), 2013.

Abstract

The tris(alkyne) copper complex [(cyclooctyne)3Cu][SbF6] has been synthesized using cyclooctyne and in situ generated CuSbF6. Tris(alkyne) silver complexes [(cyclooctyne)3Ag]+ involving weakly coordinating counterions such as [SbF6]− and [PF6]− have also been isolated in good yield using cyclooctyne and commercially available AgSbF6 and AgPF6. These coinage metal tris(alkyne) adducts have trigonal-planar metal sites. The alkyne carbon atoms and the metal site form distorted spoke-wheel (rather than upright trigonal-prismatic) structures in the solid state. In [(cyclooctyne)3Cu][SbF6], these distortions result in a propeller-like arrangement of alkynes. A cationic gold(I) complex having two alkynes has been prepared by a reaction of equimolar amounts of Au(cyclooctyne)2Cl and AgSbF6 in dichloromethane. The gold atom of [(cyclooctyne)2Au]+ coordinates to the cyclooctynes in a linear fashion, while the carbon atoms of the alkyne groups form a tetrahedron around gold(I). Optimized geometries of cationic [(cyc...

Details

ISSN :
15206041 and 02767333
Volume :
32
Database :
OpenAIRE
Journal :
Organometallics
Accession number :
edsair.doi...........fe8f34ed11148f9c8e8f2fec20177304
Full Text :
https://doi.org/10.1021/om400073a