The redox chemistry of akyne-trimetal clusters has been investigated by electrochemical and spectroscopic techniques. The closo-Fe3(CO)9(RC2R) series undergoes two near reversible one-electron reduction steps. The bulk of spectroscopic data of the electrolytically generated [Fe3(CO)9(EtC2Et)]2- dianion strongly suggests that the orientation of the alkyne moiety relative to the metallic triangle is changed from perpendicular to parallel. On the contrary the cathodic reduction of the nido series FeCo2(CO)9(EtC2Et), Os3(CO)10(EtC2Et), and H2M3(CO)9(EtC2Et) (M = Ru, Os) is totally irreversible and is associated to cluster breakdown.
Reorientation of the alkyne moiety in Fe3(CO)9(RC2R) Clusters induced by a two-electron Electochemical Reduction
OSELLA, Domenico;GOBETTO, Roberto;
1986-01-01
Abstract
The redox chemistry of akyne-trimetal clusters has been investigated by electrochemical and spectroscopic techniques. The closo-Fe3(CO)9(RC2R) series undergoes two near reversible one-electron reduction steps. The bulk of spectroscopic data of the electrolytically generated [Fe3(CO)9(EtC2Et)]2- dianion strongly suggests that the orientation of the alkyne moiety relative to the metallic triangle is changed from perpendicular to parallel. On the contrary the cathodic reduction of the nido series FeCo2(CO)9(EtC2Et), Os3(CO)10(EtC2Et), and H2M3(CO)9(EtC2Et) (M = Ru, Os) is totally irreversible and is associated to cluster breakdown.
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