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Aza versus Oxophilicity of SmI2 : A Break of a Paradigm
Sandeepan Maity1,2, Robert A Flowers1, Shmaryahu Hoz2
1Department of Chemistry, Lehigh University, 6 E Packer Ave., Bethlehem, Pennsylvania-, 18015, USA.
Abstract:
Ligands that coordinate to SmI2 through oxygen are prevalent in the literature and make up a significant portion of additives employed with the reagent to perform reactions of great synthetic importance. In the present work a series of spectroscopic, calorimetric and kinetic studies demonstrate that nitrogen-based analogues of many common additives have a significantly higher affinity for Sm than the oxygen-based counterparts. In addition, electrochemical experiments show that nitrogen-based ligands significantly enhance the reducing power of SmI2 . Overall, this work demonstrates that the use of nitrogen-based ligands provides a useful alternative approach to enhance the reactivity of reductants based on SmII .
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