Thermal Dissociation of N,N-Dimethylformamide–Tetracyanoethylene and Dimethyl Sulfoxide–Tetracyanoethylene Complexes into Ions

Ionic dissociation of N,N-dimethylformamide (DMF)–tetracyanoethylene (TCNE) and dimethyl sulfoxide (DMSO)–TCNE electron donor-acceptor (EDA) complexes was studied by means of optical absorption and electron spin resonance measurements. Upon dissolving TCNE into DMF or DMSO, essentially all the TCNE became complexed with the electron-donationg solvent; charge-transfer bands with maxima at 310 and 380 nm were found for DMF–TCNE and DMSO–TCNE complexes, respectively. The CT bands were transformed slowly in the dark into the band of TCNE−. This transformation proceeded quantitatively and indicated the dissociation of the EDA complexes into ions. The rate of the ionic dissociation was determined by following a first-order growth of the ESR spectrum of TCNE− at various temperatures: k=108.9exp(79⁄RT) for the DMF–TCNE complex and k=106.3exp(59⁄RT) for the DMSO–TCNE complex, in units of s and kJ/mol. Dissolved oxygen was found not only to react chemically with the complex to form a new stable species, but also to...

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