25022-93-9Relevant academic research and scientific papers
Hypovalent Radicals. Chemical Trapping of Electrogenerated Diazoalkane Anion Radicals
Triebe, F. M.,Hawley, M. Dale,McDonald, Richard N.
, p. 574 - 575 (2007/10/02)
Diazoalkane anion radicals produced by electroreduction of diazodiphenylmethane (Ph2CN2) and 9-diazofluorene (FlN2) in the presence of certain proton donors yield the corresponding hydrazones (R2C=NNH2); formation of diphenylmethane from electroreduction of Ph2CN2 is shown to proceed by formation of the carbene anion radical Ph2C*-.
Hypovalent Radicals. 6. Electroreduction of Diazodiphenylmethane-Intermediacy of Ph2CN-. and PhC-.
McDonald, Richard N.,Triebe, F. M.,January, J. R.,Borhani, K. J.,Hawley, M. D.
, p. 7867 - 7872 (2007/10/02)
The electrochemical reduction of diazodiphenylmethane (Ph2CN2) at a platinum cathode in DMF-0.1 F (n-Bu)4ClO4 has been shown to afford benzophenone azine ((Ph2C=N-)2) as the principal product, along with lesser amounts of Ph2CH2 and several other compounds.Product formation occurs by a chain process in which the carbene anion radical, Ph2C-., is produced from electrogenerated Ph2CN2-. by rapid loss of nitrogen.Ph2CH-, the first-observed intermediate in Ph2CN2 electroreduction, is obtained from Ph2C-. either by protonation followed by reduction or by hydrogen atom abstraction from a component of the solvent-electrolyte system.Propagation of the chain involves coupling of Ph2CH- with Ph2CN2 to produce Ph2CHN=CPh2 followed by proton transfer from this anion to Ph2C-. to give (Ph2C=N-)22- and Ph2CH., respectively.Regeneration of Ph2CN2-. occurs by electron transfer from either (Ph2C=N-)22- or (Ph2C=N-)2-. to Ph2CN2.Termination of the chain occurs upon protonation of Ph2CH-.In the presence of the electroinactive proton donors, diethyl malonate and 2,2,2-trifluoroethanol, azine formation is interdicted and Ph2C=NNH2 and Ph2CH2 are the two major products.Studies of the Ph2CH2/Ph2C=NNH2 product ratio as a function of proton donor concentration and temperature have established that protonation (and other reactions) of Ph2CN2-. occurs exclusively on terminal nitrogen while Ph2CH2 arises via Ph2C-..No evidence was obtained for either hydrogen atom abstraction by or protonation of Cα of Ph2CN2-..
Radical Anions in the Reduction of Benzophenone Azine
Handoo, Kishan L.,Handoo, Sudesh K.
, p. 684 - 687 (2007/10/02)
Cyclic voltammetric reduction of benzophenone azine produces radical anions and dianions in two reversible one-electron steps in dimethylformamide.A similar sequence of reaction occurs when the azine is reduced with sodium naphthalenide in degassed tetrahydrofuran.ESR-spectrum is reported for the radical anion and the scope of the reaction leading to the products of electron-transfer reduction with sodium naphthalenide has been investigated.
