Issue 5, 2012

Infrared photodissociation spectra of mass selected homoleptic dinuclear iron carbonyl cluster anions in the gas phase

Abstract

Infrared spectra of mass-selected homoleptic dinuclear iron carbonyl cluster anions Fe2(CO)n (n = 4–9) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The cluster anions are produced via a laser vaporization supersonic cluster source. Density functional calculations have been performed and the calculated vibrational spectra are compared to the experimental data to identify the gas-phase structures of the cluster anions. The experimentally observed Fe2(CO)n (n = 4–7) cluster anions are characterized to have unusual asymmetric (OC)4Fe–Fe(CO)n−4 structures, which also correspond to the computed lowest energy structures. The experimentally observed Fe2(CO)8 cluster anion is determined to have an unbridged structure instead of the previously reported dibridged structure. The Fe2(CO)9 cluster anion is determined to involve a Fe2(CO)8 core anion that is solvated by an external CO molecule. Bonding analysis indicates that these anions each have a Fe–Fe single bond to satisfy the 18-electron configuration of one iron center. The results provide important new insight into the structure and bonding mechanisms of transition-metal carbonyl clusters.

Graphical abstract: Infrared photodissociation spectra of mass selected homoleptic dinuclear iron carbonyl cluster anions in the gas phase

Supplementary files

Article information

Article type
Edge Article
Submitted
28 Jan 2012
Accepted
29 Feb 2012
First published
29 Feb 2012

Chem. Sci., 2012,3, 1698-1706

Infrared photodissociation spectra of mass selected homoleptic dinuclear iron carbonyl cluster anions in the gas phase

C. Chi, J. Cui, Z. H. Li, X. Xing, G. Wang and M. Zhou, Chem. Sci., 2012, 3, 1698 DOI: 10.1039/C2SC20119D

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