First solvation shell of the Cu(II) aqua ion: Evidence for fivefold coordination

Citation
A. Pasquarello et al., First solvation shell of the Cu(II) aqua ion: Evidence for fivefold coordination, SCIENCE, 291(5505), 2001, pp. 856-859
Citations number
31
Categorie Soggetti
Multidisciplinary,Multidisciplinary,Multidisciplinary
Journal title
SCIENCE
ISSN journal
00368075 → ACNP
Volume
291
Issue
5505
Year of publication
2001
Pages
856 - 859
Database
ISI
SICI code
0036-8075(20010202)291:5505<856:FSSOTC>2.0.ZU;2-9
Abstract
We determined the structure of the hydrated Cu(II) complex by both neutron diffraction and first-principles molecular dynamics, In contrast with the g enerally accepted picture, which assumes an octahedrally solvated Cu(II) io n, our experimental and theoretical results favor fivefold coordination. Th e simulation reveals that the solvated complex undergoes frequent transform ations between square pyramidal and trigonal bipyramidal configurations. We argue that this picture is also consistent with experimental data obtained previously by visible near-infrared absorption, x-ray absorption near-edge structure, and nuclear magnetic resonance methods. The preference of the C u(II) ion for fivefold instead of sixfold coordination, which occurs for ot her cations of comparable charge and size, results from a Jahn-Teller desta bilization of the octahedral complex.