Weakly coordinating anions (WCAs) such as [B(C6F5)4]- and [B(C6H3(CF3)2)4]- have generated a great deal of interest because of certain well-established advantages over traditional anions (e.g. PF6- and BF4-). One of the most unusual properties of WCA salts is their very low nucleophilicity which makes possible new approaches to organometallic anodic electrochemistry. The stabilization of organometallic 17-electron radical cations, [Mn(Cp')(CO)3]+[WCA]- [Cp' = C5H5 (1, E0 = 0.92 V vs Fc0/+1), C5H4-NH2 (2, E0 = 0.60 V), and C5Me5 (3, E0 = 0.65 V)], has allowed the characterization (ESR and IR) of both the radicals (1-3) and, for Re(C5H5)(CO)3 (E0 = 1.16 V), the unusual oxidative dimerized product, [Re(C5H5)(CO)3]22+. It will be demonstrated that electrochemical reduction of a diazotized cyclopentadienyl-manganase-carbonyl, [Mn(C5H4-N2+)(CO)3]+, results in the direct covalent attachment of a cyclopentadienyl group to electrode surfaces (carbon, platinum).
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Back to The 33rd Northeast Regional Meeting (July 14-17, 2005)