An unusual equilibrium chlorine atom transfer process and its potential for assessment of steric pressure by bulky aryls.
An unusually facile intermolecular chlorine atom transfer process has been discovered between the phospha-Wittig reagents ArP=PMe3 and ArPCl2 (Ar is a sterically hindered aryl group). The atom transfer process is catalyzed by added PMe3. A mechanism is forwarded that is based upon a Me3P/Me3PCl2 couple that allows shuttling of chlorine atoms between ArP groups. This unique transfer process is exploited to evaluate the steric properties of aryl groups via an equilibrium process.
Smith
Rhett C
RC
Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106-7078, USA.
Shah
Shashin
S
Urnezius
Eugenijus
E
Protasiewicz
John D
JD