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Updated: Jun 23, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Electron transfer within charge-localized arylhydrazine-centered mixed valence radical cations having larger bridges
Stephen F Nelsen1, Kevin P Schultz
1Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706-1396, USA.
Abstract:
Kinetics for intramolecular charge transfer between two diarylhydrazine units, measured by ESR, are reported for six charge-localized mixed valence compounds having 9, 11, 13, and 16 bonds between the nitrogen atoms. A 17-bond bridged compound had too slow electron transfer to measure the rate constant by ESR. The optical spectra of these radical cations are compared with tert-butyl,aryl-substituted hydrazines, and rate constants calculated using parameters derived from the optical spectra are compared with the experimental values where possible. The charge-transfer band overlapped too badly with bridge-centered absorption for the 16-bond bridged compound to allow the comparison to be made. The 13-bond bridged compound gave worse agreement than the other compounds. Its optical rate constant was about 5.4 times the ESR rate constant at a temperature between the ranges in which the data were collected.
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