TITLE

Collision-induced dissociation and photodetachment of singly and doubly charged anionic polynuclear transition metal carbonyl clusters: Ru[sub 3]Co(CO)[sub 13][sup -], Ru[sub 6]C(CO)[sub 16][sup 2-], and Ru[sub 6](CO)[sub 18][sup 2-]

AUTHOR(S)
Butcher, Colin P. G.; Johnson, Brian F. G.; McIndoe, J. Scott; Yang, Xin; Wang, Xue-Bin; Wang, Lai-Sheng
PUB. DATE
April 2002
SOURCE
Journal of Chemical Physics;4/15/2002, Vol. 116 Issue 15, p6560
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Three polynuclear transition metal carbonyl cluster anions, Ru[sub 3]Co(CO)[sub 13][sup -], Ru[sub 6]C(CO)[sub 16][sup 2-], and Ru[sub 6](CO)[sub 18][sup 2-] have been studied using energy-dependent electrospray ionization mass spectrometry (EDESI–MS) and photodetachment photoelectron spectroscopy (PES). EDESI–MS maps show a simple collision-induced dissociation (CID) process for Ru[sub 3]Co(CO)[sub n][sup -] by stripping CO down to the metal core. For the doubly charged species, two competing CID channels were observed, viz. loss of neutral CO and loss of CO+e[sup -]. It was found that the parent dianions first lose neutral CO down to n=9, producing a series of dianions, Ru[sub 6]C(CO)[sub n][sup 2-] (n=9–16) and Ru[sub 6](CO)[sub n][sup 2-] (n=9–18). For n<9, the dianions become electronically unstable against autodetachment, and singly charged anions, Ru[sub 6]C(CO)[sub n][sup -] and Ru[sub 6](CO)[sub n][sup -] (n=0–9), were observed. The PES spectra of the dianions show the electron binding energies decrease monotonically as n decreases and become ∼0.0 eV for n=9, in exact agreement with the CID patterns that reflect the electronic instability of the doubly charged metal complexes with n<9. All of the PES spectra show congested features, indicating very high density of low-lying electronic states for the transition metal carbonyl clusters. The electron binding energies of Ru[sub 3]Co(CO)[sub n][sup -] are similar for n=4–13, but decrease sharply from n=4 to 0. The intramolecular Coulomb repulsion in the dianions was observed to increase with loss of CO, ranging from ∼1.8 eV for Ru[sub 6]C(CO)[sub 16][sup 2-] to ∼2.4 eV for Ru[sub 6]C(CO)[sub 9][sup 2-]. © 2002 American Institute of Physics.
ACCESSION #
6427023

 

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