Cation-π and CH-π interactions in the coordination and solvation of Cu+ (acetylene)n (n=1-6) complexes investigated via infrared photodissociation spectroscopy

Brathwaite, Antonio David

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https://hdl.handle.net/2142/79338 Copy

Description

Title

Cation-π and CH-π interactions in the coordination and solvation of Cu+ (acetylene)n (n=1-6) complexes investigated via infrared photodissociation spectroscopy

Author(s)

Brathwaite, Antonio David

Contributor(s)

• Duncan, Michael A.
• WARD, TIMOTHY B
• Walters, Richard S.

Issue Date

25-Jun-15

Keyword(s)

Metal containing

Abstract

Mass-selected copper-acetylene cation complexes of the form Cu(C$_{2}$H$_{2}$)$_{n}$+ are produced by laser ablation and studied via infrared laser photodissociation spectroscopy in the C-H stretching region (3000-3500 wn). Spectra for larger species are measured via ligand elimination, whereas argon tagging is employed to enhance dissociation yields in smaller complexes. The number of infrared active bands, their frequency positions and their relative intensities provide insight into the structure and bonding of these ions. Density functional theory calculations are carried out in support of this work. The combined data show that cation-$pi$ bonds are formed for the n=1-3 species, resulting in red-shifted C-H stretches on the acetylene ligands. Three acetylene ligands complete the coordination of the copper cation. Additional ligands (n=4-6) solvate the n=3 core by forming CH-$pi$ bonds. Distinctive vibrational patterns are exhibited for coordinated vs. solvent ligands. Theory reproduces these results.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/79338

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