Citation:
Abstract:
The previously unknown radical anions of unsaturated E2N4S2 ring systems (E = RC, R2NC, R2P) can be generated voltammetrically by the one-electron reduction of the neutral species and, despite half-lives on the order of a few seconds, have been unambiguously characterized by electron paramagnetic resonance (EPR) spectroelectrochemistry using a highly sensitive in situ electrolysis cell. Cyclic voltammetric studies using a glassy-carbon working electrode in CH3CN and CH2Cl2 with [(Bu4N)-Bu-n][PF6] as the supporting electrolyte gave reversible formal potentials for the [E2N4S2](0/-) process in the range of -1.25 to -1.77 V and irreversible peak potentials for oxidation in the range of 0.66 to 1.60 V (vs the Fc(+/0) couple; Fc = ferrocene). Reduction of the neutral compound undergoes an electrochemically reversible one-electron transfer, followed by the decay of the anion to an unknown species via a first-order (chemical) reaction pathway. The values of the first-order rate constant, k(f), for the decay of all the radical anions in CH2Cl2 have been estimated from the decay of the EPR signals for (X-C6H4CN2S)(2)(center dot-), where X = 4-OCH3 (k(f) = 0.04 s(-1)), 4-CH3 (k(f) = 0.02 s(-1)), 4-H (k(f) = 0.08 s(-1)), 4-Cl (k(f) = 0.05 s(-1)), 4-CF3 (k(f) = 0.05 s(-1)), or 3-CF3 (k(f) = 0.07 s(-1)), and for [(CH3)(3)CCN2S](2)(center dot-) (k(f) = 0.02 s(-1)), [(CH3)(2)NCN2S](2)(center dot-) (k(f) = 0.05 s(-1)), and [(C6H5)(2)PN2S](2)(center dot-) (k(f) = 0.7 s(-1)). Values of k(f) for X = 4-H and for [(CH3)(2)NCN2S](2)(center dot-) were also determined from the cyclic voltammetric responses (in CH2Cl2) and were both found to be 0.05 s(-1). Possible pathways for the first-order anion decomposition that are consistent with the experimental observations are discussed. Density functional theory calculations at the UB3LYP/6-31G(d) level of theory predict the structures of the radical anions as either planar (D-2h) or folded (C-2v) species; the calculated hyperfine coupling constants are in excellent agreement with experimental results. Linear correlations were observed between the voltammetrically determined potentials and both the orbital energies and Hammett coefficients for the neutral aryl-substituted rings.
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Times Cited: 12Boere, Rene T. Bond, Alan M. Chivers, Tristram Feldberg, Stephen W. Roemmele, Tracey L.