Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2-2008

Journal or Book Title

Journal of Physical Chemistry A

Volume

112

Issue

9

First Page

1907

Last Page

1913

DOI

10.1021/jp711099u

Abstract

Au+(CO)n complexes are produced in the gas phase via pulsed laser vaporization, expanded in a supersonic jet, and detected with a reflectron time-of-flight mass spectrometer. Complexes up to n = 12 are observed, with mass channels corresponding to the n = 2 and n = 4 showing enhanced intensity. To investigate coordination and structure, individual complexes are mass-selected and probed with infrared photodissociation spectroscopy. Spectra in the carbonyl stretching region are measured for the n = 3−7 species, but no photodissociation is observed for n = 1, 2 due to the strong metal cation-ligand binding. The carbonyl stretch in these systems is blue-shifted 50−100 cm-1 with respect to the free CO vibration (2143 cm-1), providing evidence that these species are so-called “nonclassical” metal carbonyls. Theory at the MP2 and CCSD(T) levels provides structures for these complexes and predicted spectra to compare to the experiment. Excellent agreement is obtained between experiment and theory, establishing that the n = 3 complex is trigonal planar and the n = 4 complex is tetrahedral.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 112 (2008): 1907, doi:10.1021/jp711099u. Copyright 2008 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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