Deng Guohai, Reimann Marc, Meyer Deniz, Xia Xiya, Kaupp Martin, Riedel Sebastian
Institut für Chemie und Biochemie-Anorganische Chemie, Freie Universität Berlin, Fabeckstrasse 34/36, Berlin 14195, Germany.
Institut für Chemie, Theoretische Chemie/Quantenchemie, Technische Universität Berlin, Sekr. C7, Strasse des 17. Juni 135, Berlin 10623, Germany.
J Am Chem Soc. 2024 Aug 28;146(34):23972-23977. doi: 10.1021/jacs.4c07079. Epub 2024 Aug 15.
Terminal oxygen radicals involving p- and d-block atoms are quite common, but s-block compounds with an oxygen radical character remain rare. Here, we report that alkaline-earth metal beryllium atoms react with OF to form the oxygen beryllium fluorides OBeF and OBeF. These species are characterized by matrix-isolation infrared spectroscopy with isotopic substitution and quantum-chemical calculations. The linear molecule OBeF has a Π ground state with an oxyl radical character. The A () ground state of OBeF represents the unusual case of a triplet oxygen atom stabilized by a relatively weak interaction by the Lewis acidic BeF. The interaction involves both a donor component from oxygen to empty Be orbitals and a back-bonding contribution from fluorine substituents toward oxygen.
涉及p族和d族原子的末端氧自由基相当常见，但具有氧自由基特征的s族化合物仍然很少见。在此，我们报告碱土金属铍原子与OF反应形成氧铍氟化物OBeF和OBeF。这些物种通过同位素取代的基质隔离红外光谱和量子化学计算进行表征。线性分子OBeF具有具有氧基自由基特征的Π基态。OBeF的A（）基态代表了一个不寻常的情况，即三重态氧原子通过与路易斯酸性BeF的相对较弱相互作用而稳定。这种相互作用既包括从氧到铍空轨道的供体成分，也包括氟取代基对氧的反馈键贡献。
