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Title: Synthesis, Structure, and Electrochemistry of the Dicluster Molecular Pincer [Pt3(μ-PBut2)3(CO)2]2(μ-1′,1′′′-diethynylbiferrocene)
Authors: Albinati, A.
Balzano, F.
Fabrizi De Biani, Fabrizia 
Leoni, P.
Manca, G.
Marchetti, L.
Rizzato, S.
Uccello Barretta, G.
Zanello, Piero
Issue Date: 2010
Project: None 
The CuI catalyzed dehydro-halogenation of 1′,1′′′-diethynylbiferrocene and {Pt3}Cl [{Pt3} = Pt3(μ-PBut2)3(CO)2] (1:2 molar ratio) in diethylamine gives in high yields the bicluster derivative [{Pt3}CC-(η5-C5H4)Fe(η5-C5H4)]2, 3, in which two platinum triangles are connected by a diethynylbiferrocene spacer. In the structure of 3, confirmed by a diffractometric study, the two {Pt3} fragments lie, perfectly eclipsed, on the same side of the biferrocenyl moiety; this folded structure is also preferred in solution, as suggested by NMR Diffusion Ordered Spectroscopy (DOSY) and 1D Rotating-frame Overhauser Enhancement (ROE) measurements. Compound 3 exhibits a rich redox behavior, with a crowded sequence of six one-electron oxidation processes, the electrode potentials of which have been evaluated by digital simulations. On the basis of a spectroelectrochemical study, the first two oxidations are assigned to the iron centers of the diferrocenyl unit and the subsequent four electrons are removed from the {Pt3} units.
ISSN: 0020-1669
DOI: 10.1021/ic9014459
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