The 62-CVE clusters Ru-4(mu-RC2R)(2)(CO)(11), which feature a dodecahedral cluster core, are readily reduced to a 64-CVE dianion in a process that is essentially chemically reversible. A combination of electrochemical, spectroelectrochemical, and computational analyses of the system indicates that the first formed dianion, which features a square planar arrangement of the metal centers with the alkyne ligands located on opposite faces of the M-4 square and oriented in a manner such that the C-C bonds are perpendicular to each other, undergoes a thermal rearrangement giving a product in which the alkyne vectors lie parallel to each other across the metal framework.
A combined spectroelectrochemical and computational study of the chemically reversible 2-electron reduction of [Ru-4(mu-RC2R)(2)(CO)(11)] clusters
NERVI, Carlo;
2005-01-01
Abstract
The 62-CVE clusters Ru-4(mu-RC2R)(2)(CO)(11), which feature a dodecahedral cluster core, are readily reduced to a 64-CVE dianion in a process that is essentially chemically reversible. A combination of electrochemical, spectroelectrochemical, and computational analyses of the system indicates that the first formed dianion, which features a square planar arrangement of the metal centers with the alkyne ligands located on opposite faces of the M-4 square and oriented in a manner such that the C-C bonds are perpendicular to each other, undergoes a thermal rearrangement giving a product in which the alkyne vectors lie parallel to each other across the metal framework.
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