Bonding Analysis of Square-Antiprismatic and Fused Square-Antiprismatic Copper(I)-Selenium Clusters
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Date
2004
Journal Title
Journal ISSN
Volume Title
Publisher
Journal of Cluster Science
Abstract
The electronic structure of the Cu2(4n+2)Se4n+2(PH3)8 (n = 1–4) D4h series of
model clusters has been analyzed by means of density functional theory calculations.
The fused square antiprismatic structure of the metal framework is
found to be always preferred over the fused cuboctahedral one because it reinforces
the Cu-P bonds. Thus, the presence of the terminal phosphine ligands
tends to strengthen the Cu…Cu (d10… d10) bonding by mixing bonding combinations
of the vacant Cu 4s and 4p orbitals into the occupied 3d combinations.
The calculations indicate that the compounds corresponding to n = 3 and 4
should be easily two-electron-reduced, leading to stable dianionic specie
Description
Keywords
Density functional theory, copper(I)-selenium clusters