The role of ligand displacement in SmII-HMPA-based reductions
Edamana Prasad1, Brian W Knettle, Robert A Flowers
1Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA.
Abstract:
Addition of HMPA to [Sm[N(SiMe(3))(2)](2)] produces a less reactive reductant in contrast to addition of HMPA to SmI(2). While the [Sm[N(SiMe(3))(2)](2)]-HMPA combination results in a more powerful reductant based on the redox potential, the observed decrease in reactivity is attributed to steric hindrance caused by the nonlabile ligand -N(SiMe(3))(2) and HMPA around the Sm metal. The importance of ligand displacement (exchange) in Sm(II)-HMPA-based reactions and insight into the mechanism of [Sm[N(SiMe(3))(2)](2)]-HMPA and SmI(2)-HMPA reductions are presented.
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