The role of ligand displacement in SmII-HMPA-based reductions |
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Authors: | Prasad Edamana Knettle Brian W Flowers Robert A |
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Institution: | Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA. |
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Abstract: | Addition of HMPA to SmN(SiMe(3))(2)](2)] produces a less reactive reductant in contrast to addition of HMPA to SmI(2). While the SmN(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 SmN(SiMe(3))(2)](2)]-HMPA and SmI(2)-HMPA reductions are presented. |
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