Task-Dependent Coordination Levels of SmI 2

Ligation plays a multifaceted role in the chemistry of SmI . Depending on the ligand, two of its major effects are increasing the reduction potential of SmI , and in the case of a ligand, which is also a proton donor, it may also enhance the reaction by protonation of the radical anion generated in the preceding step. It turns out that the number of ligand molecules that are needed to maximize the reduction potential of SmI is significantly smaller than the number of ligand molecules needed for a maximal enhancement of the protonation rate. In addition to the economical use of the ligand, this information can also be utilized as a diagnostic tool for the reaction mechanism in differentiating between single and multistep processes. The possible pitfalls in applying this diagnostic tool to PCET and cyclization reactions are discussed.