INOR Bernadette Donovan-Merkert, Michelle Millar  Sunday, March 21, 2010 

445 - Electrochemistry and reactivity of bis(phosphino)cobaltocinium compounds

Kyle D. Reichl1,, Chip Nataro1, W. Scott Kassel2, William G Dougherty2. (1) Department of Chemistry, Lafayette College, Easton, PA 18042, United States, (2) Department of Chemistry, Villanova University, Villanova, PA 19085, United States

The electrochemistry of two bis(phosphino)cobaltocenes,
1,1'-bis(diphenylphosphino)cobaltocenium hexafluorophosphate ([dppc][PF6])
and 1,1'-bis(dicyclohexylphosphino)cobaltocenium hexafluorophosphate ([dcpc][PF6]),
was examined in methylene chloride with tetrabutylammonium hexafluorophosphate
as the supporting electrolyte. Several new chalcogenide derivatives,
[dppcS2][PF6], [dppcSe2][PF6],
[dcpcS2][PF6], and [dcpcSe2][PF6],
were prepared, characterized, and analyzed by cyclic voltammetry. Reduction of
each of these compounds resulted in two electrochemically reversible waves,
likely due to the Co3+ center. Oxidation of the oxide and sulfide
derivatives yielded no discernable electrochemistry, whereas the oxidation of
both [dppcSe2][PF6] and [dcpcSe2][PF6]
resulted in an electrochemically irreversible wave. Three new transition metal
complexes in which [dppc][PF6] and [dcpc][PF6] were bound
to PdCl2, PtCl2, and (AuCl)2 were also
prepared and characterized. Electrochemical analysis of the [dcpc][PF6] complexes clearly indicated that coordination
resulted in more positive reduction potentials for the cobaltocenium ligand.

Sunday, March 21, 2010 07:00 PM
Organometallic Chemistry: Synthesis and Characterization (07:00 PM - 09:00 PM)
Location: The Moscone Center
Room: Hall D


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