Jobbins William D, Cullen Rory T, Stott Thomas, van IJzendoorn Bono, Réant Benjamin L L, Johnstone Timothy C, Mehta Meera
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, U.K.
Inorg Chem. 2024 Jul 29;63(30):13807-13814. doi: 10.1021/acs.inorgchem.4c02264. Epub 2024 Jul 16.
In this work, the reactivity of tetrel-functionalized phosphorus clusters toward organoazides is probed. Clusters (MeSi)P () and (MeGe)P () 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 N 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 -nitrogen-bonded moieties, which, to the best of our knowledge, were previously unknown.
在这项工作中，研究了四价元素官能化的磷簇对有机叠氮化物的反应活性。使簇合物（MeSi）P（）和（MeGe）P（）与苄基叠氮、苯基叠氮和4-溴苯基叠氮反应，发现叠氮化物中的[RN]（R = 苄基、苯基和4-溴苯基）单元插入到簇合物上的磷-四价元素键中，并伴有氮的消除。通过控制叠氮化物的化学计量，可以观察到单插入、双插入和三插入产物，这与这些插入反应以逐步方式进行一致。通过计算化学进一步研究了胺部分与簇合物之间的键合，结果与磷簇经历了形式上的氧化一致。这些插入反应是获得用氮键合部分官能化的齐特耳簇的便捷方法，据我们所知，此前这些簇是未知的。
