Reactivity of Tetrel-Functionalized Heptaphosphane Clusters toward Azides

Journal article

In this work, the reactivity of tetrel-functionalized phosphorus clusters toward organoazides is probed. Clusters (Me3Si)3P7 (1) and (Me3Ge)3P7 (2) were reacted with benzyl azide, phenyl azide, and 4-bromophenyl azide, and it was found that the [RN] (R = benzyl, phenyl, and 4-bromophenyl) unit from the azide inserted into the phosphorus–tetrel bonds on the cluster, accompanied by N2 elimination. Through control of the azide stoichiometry, the mono-, bis-, and tris-inserted 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.

Authors: Jobbins, WD; Cullen, RT; Stott, T; van IJzendoorn, B; Réant, BLL

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Inorganic Chemistry
• Volume: 63
• Issue: 30
• Pages: 13807-13814
• Publication date: 2024-07-16
• Acceptance date: 2024-06-20
• DOI: 10.1021/acs.inorgchem.4c02264
• EISSN: 1520-510X
• ISSN: 0020-1669
• Language: English