title: Reductions with SmI2: mechanistic probe for distinguishing between two operational modes of proton transfer.
abstract: The reduction of 1,1-diaryl-2,2-dicyanoethylenes with SmI(2) in THF was studied in the presence of four proton donors: H(2)O, MeOH, i-PrOH and trifluoroethanol (TFE). The kinetic order for the first two is nearly unity at low proton donor concentrations and approaches four at high concentrations, whereas, for i-PrOH and TFE, the log-log plot is linear with a slope smaller than one. Detailed analysis shows that a curved log-log plot such as for H(2)O and MeOH is indicative of a major contribution by protonation within an ion pair of the radical anion and Sm(+3) complexed to a variable number of proton donor molecules, whereas a linear plot is a result of protonation from the bulk solution.
authors.affiliation: Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel.
authors.forename: Alexander
authors.initials: A
authors.lastname: Tarnopolsky
authors.forename: Shmaryahu
authors.initials: S
authors.lastname: Hoz