Xia Xiya, Medel Robert, Riedel Sebastian
Institut für Chemie und Biochemie - Anorganische Chemie, Freie Universität Berlin, Fabeckstraße 34/36, 14195, Berlin, Germany.
Angew Chem Int Ed Engl. 2025 Aug 25;64(35):e202507151. doi: 10.1002/anie.202507151. Epub 2025 Jul 16.
Side-on coordinated molecular hypofluorites FM(η-OF) (M = Mg, Ca, Sr, and Ba) were prepared by co-deposition of laser-ablated alkaline earth metal atoms with diluted OF in cryogenic matrices. The structures parallel the non-VESPR structures of alkaline earth metal difluorides and dihydrides, such that FMg(η-OF) is planar, FCa(η-OF) is planar but with a shallow bending-potential curve, while FSr(η-OF) and FBa(η-OF) are non-planar. Bonding analyses show that the interactions between the metal center M and the negatively charged ligands F and OF are mainly electrostatic. Moreover, for FMg(η-OF), donation of electron density from OF to empty s and p orbitals of magnesium is involved. However, for the heavier alkaline earth metal compounds, the donation to empty d orbitals of the metal center becomes dominant in orbital interactions, which contributes to their non-planar structures.
通过在低温基质中将激光烧蚀的碱土金属原子与稀释的OF共沉积，制备了侧配位的分子次氟化物FM(η-OF)（M = Mg、Ca、Sr和Ba）。其结构与碱土金属二氟化物和二氢化物的非VESPR结构相似，使得FMg(η-OF)是平面的，FCa(η-OF)是平面的但具有浅的弯曲势曲线，而FSr(η-OF)和FBa(η-OF)是非平面的。键合分析表明，金属中心M与带负电荷的配体F和OF之间的相互作用主要是静电作用。此外，对于FMg(η-OF)，涉及从OF向镁的空s和p轨道的电子密度捐赠。然而，对于较重的碱土金属化合物，向金属中心的空d轨道的捐赠在轨道相互作用中占主导地位，这导致了它们的非平面结构。
