Infrared spectroscopy of extreme coordination: The carbonyls of U + and UO2+

Allen M. Ricks; Laura Gagliardi; Michael A. Duncan

doi:10.1021/ja1077365

Infrared spectroscopy of extreme coordination: The carbonyls of U ⁺ and UO₂⁺

Allen M. Ricks, Laura Gagliardi, Michael A. Duncan

Chemistry (Twin Cities)

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68 Scopus citations

Abstract

Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)₈⁺ and UO₂(CO)₅⁺, with D_4d square antiprism and D_5h pentagonal bipyramid structures. Back-bonding in U(CO) ₈⁺ causes a red-shifted CO stretch, but back-donation is inefficient for UO₂(CO)₅⁺, producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.

Original language	English (US)
Pages (from-to)	15905-15907
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	132
Issue number	45
DOIs	https://doi.org/10.1021/ja1077365
State	Published - Nov 17 2010

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abstract = "Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)8+ and UO2(CO)5+, with D4d square antiprism and D5h pentagonal bipyramid structures. Back-bonding in U(CO) 8+ causes a red-shifted CO stretch, but back-donation is inefficient for UO2(CO)5+, producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.",

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AB - Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)8+ and UO2(CO)5+, with D4d square antiprism and D5h pentagonal bipyramid structures. Back-bonding in U(CO) 8+ causes a red-shifted CO stretch, but back-donation is inefficient for UO2(CO)5+, producing a blue-shifted CO stretch characteristic of nonclassical carbonyls.

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Infrared spectroscopy of extreme coordination: The carbonyls of U ⁺ and UO₂⁺

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