58468-78-3Relevant academic research and scientific papers
Sandmeyer reactions. Part 6. A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation
Hanson, Peter,Rowell, Simon C.,Taylor, Alec B.,Walton, Paul H.,Timms, Allan W.
, p. 1126 - 1134 (2002)
For Sandmeyer cyanation at 298 K in 50% v/v aqueous acetonitrile buffered at pH 8, absolute rate constants have been obtained for the reduction of 4-methoxybenzenediazonium tetrafluoroborate by the cyanocuprate(I) anions Cu1(CN)43-, Cu1(NCMe)(CN)32- and Cu1(NCMe)2(CN)2- as (0.50 ± 0.05), (0.12 ± 0.03) and 0.0 dm3 mol-1 s-1, respectively. The relative reactivity of the two reactive cyanocuprates reflects the estimated difference in their standard reduction potentials. Ligand transfer to the aryl radical from the cyanocuprate(II) anions produced in the reaction occurs within the solvent cage. By use of radical clocks, first order rate constants of the order of 1 × 108 s-1 for ligand transfer between the caged reactants can be evaluated although the transfer rate may vary from one aryl radical to another. No difference was discerned in ligand transferring reactivity between the two cyanocuprate(II) complexes involved.
UV AND IR SPECTRA OF SOME ARENEDIAZOCYANIDES AND THEIR RADICAL-ANIONS
Kachkurova, I. Ya.,Ashkinadze, L. D.,Shamsutdinova, M. Kh.,Kazitsyna, L. A.
, p. 1629 - 1634 (2007/10/02)
The UV and IR spectra of some arenediazocyanides and their radical-anions with the general formula p-X-C6H4N=NCN, where X=CH3O, CN, NO2, CNN=N, CNC6H4, NO2C6H4, CNN=NC6H4, NO2C6H4S, CNN=NC6H4O, CNN=NC6H4S, were studied.During radical formation long-wave absorption bands appear in the UV spectrum in the region of 600-700 nm.The frequencies of the absorption band for the nitrile group (Δν 80-95 cm-1) in the IR spectrum are shifted substantially.The integral intensities ACN increase by two orders of magnitude.The obtained experimental data show that during radical formation from the arenediazocyanides the additional electron is concentrated mainly at the diazocyanide group, and in the binuclear systems the effect of the anionic substituent N=NCN(1-) is not transmitted to the second benzene ring.It is suggested that the special features in the spectral characteristics of the arenediazocyanides and their radical-anions are due to the specific structural character of the azo group.
