Hydrodehalogenation of alkyl halides catalyzed by a trichloroniobium complex with a redox active α-diimine ligand
A high-valent d0 niobium(v) complex, (α-diimine)NbCl3 (1), bearing a dianionic redox-active α-diimine ligand served as a catalyst for a hydrodehalogenation reaction of alkyl halides in the presence of PhSiH3. During the catalytic reaction, the redox-active α-diimine ligand allowed the complex to reversibly release and accept one-electron through switching its coordination mode between a dianionic folded form and a monoanionic planar one.
Nishiyama, Haruka,Hosoya, Hiromu,Parker, Bernard F.,Arnold, John,Tsurugi, Hayato,Mashima, Kazushi
supporting information
p. 7247 - 7250
(2019/07/02)
Solvent pressure effects in free radical reactions. 2. Reconciliation of the gas and condensed phase chlorination of cyclopropane
The results reported herein demonstrate that the chemoselectivity (SH2 ring opening vs abstraction of a cyclopropyl hydrogen) associated with the free radical chlorination of cyclopropane is solvent dependent. Internal pressure is implicated as the solvent parameter responsible for the observed solvent effect. (Solvents of high internal pressure favor the SH2 process; hydrogen abstraction becomes more important in solvents of low internal pressure or in the gas phase.) Extrapolation of the solution phase results to zero internal pressure accurately predicts the gas-phase result, suggesting that the difference in chemoselectivity between the vapor- and condensed-phase reactions is attributable to internal pressure in the condensed phase medium. No evidence for the chlorine atom cage effect is found in the chlorination of cyclopropane.
Tanko, James M.,Suleman, N. Kamrudin
p. 5162 - 5166
(2007/10/02)
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