Zintl Clusters as a Platform for Lewis Acid Catalysis

Réant, Benjamin L. L.; Whitehead, George F. S.; Mehta, Meera

doi:10.1021/acs.inorgchem.4c00433

Cited by 1 publication

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References 83 publications

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“…There has been a reignited interest in studying the chemistry of Zintl clusters, given their interesting bonding and aesthetically pleasing architectures . Recent developments in the field have been focused on probing their coordination chemistry with transition metals to allow access to new physical properties, applying them as catalysts to mediate organic transformations, , and using them as precursors in the bottom-up solution-state synthesis of nanostructures . Although the applications of these clusters can often be tuned by functionalizing them with organic units, the number of functionalization options is unfortunately limited.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Tetrel-Functionalized Heptaphosphane Clusters toward Azides

Jobbins,

Cullen,

Stott

et al. 2024

Inorg. Chem.

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In this work, the reactivity of tetrel-functionalized phosphorus clusters toward organoazides is probed. Clusters (Me 3 Si) 3 P 7 (1) and (Me 3 Ge) 3 P 7 (2) were reacted with benzyl azide, phenyl azide, and 4-bromophenyl azide, and it was found that the [RN] (R = benzyl, phenyl, and 4bromophenyl) unit from the azide inserted into the phosphorus−tetrel bonds on the cluster, accompanied by N 2 elimination. Through control of the azide stoichiometry, the mono-, bis-, and trisinserted products could be observed, consistent with these insertions proceeding in a stepwise manner. The bonding between the amine moieties and clusters was further investigated by computational chemistry, and the findings were consistent with the phosphorus cluster having undergone a formal oxidation. These insertion reactions are a convenient means of accessing Zintl clusters functionalized with exo-nitrogen-bonded moieties, which, to the best of our knowledge, were previously unknown.

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