Wei Rui, Fang Zongtang, Vasiliu Monica, Dixon David A, Andrews Lester, Gong Yu
Department of Radiochemistry , Shanghai Institute of Applied Physics, Chinese Academy of Sciences , Shanghai 201800 , China.
School of Nuclear Science and Technology , University of Chinese Academy of Sciences , Beijing 100049 , China.
Inorg Chem. 2019 Aug 5;58(15):9796-9810. doi: 10.1021/acs.inorgchem.9b00822. Epub 2019 Jul 15.
A collection of 3d transition metal (V, Mn, Fe, Co, and Ni) oxyfluorides were prepared via the reactions of laser-ablated metal atoms and OF in an argon matrix, and the products were identified by infrared spectroscopy together with OF substitution. OMF is the major product from the reactions of metal atoms and OF. The tetravalent metal center is coordinated to two fluorine atoms and one oxygen atom. Triatomic OMF molecules were observed in the reactions of V, Mn, Fe, and Co with OF. In addition to OMF and OMF, OMnF and OFeF were also formed presumably via the reactions of OMnF and OFeF with F resulting from photodecomposition of OF. The seldom observed OF radical was produced in all of these experiments. Electronic structure calculations at the density functional theory and molecular orbital theory including electron correlation effects (CCSD(T) and CASPT2) levels are used to aid in the assignment of the structures. For OMF (M = Sc-Mn), the structures are bent and those for M = Fe-Cu are linear. The OMF molecules are optimized to be structures. Both OMF and OMF have a high spin ground state, with the exception of OCoF in which the ground state quartet is the lower energy structure. The M-O stretching frequency is a sensitive measure of the computational method in terms of the bond angle, the coupling of the M-O and M-F stretches, and the amount of spin on the oxygen. A bonding analysis in terms of the CAS orbitals shows that a number of the structures have a multireference character after M = Cr. Oxidation states of the metal are given based on the CASPT2 results. Heats of formation for the OMF and OMF are reported.
通过激光烧蚀金属原子与氩气基质中的OF反应制备了一系列3d过渡金属（V、Mn、Fe、Co和Ni）的氟氧化物，并通过红外光谱结合OF取代对产物进行了鉴定。OMF是金属原子与OF反应的主要产物。四价金属中心与两个氟原子和一个氧原子配位。在V、Mn、Fe和Co与OF的反应中观察到了三原子OMF分子。除了OMF和OMF外，OMnF和OFeF可能也是由OMnF和OFeF与OF光解产生的F反应形成的。在所有这些实验中都产生了很少被观察到的OF自由基。使用密度泛函理论和分子轨道理论（包括电子相关效应（CCSD(T)和CASPT2）水平）的电子结构计算来辅助结构的归属。对于OMF（M = Sc - Mn），结构是弯曲的，而M = Fe - Cu时结构是线性的。OMF分子被优化为结构。除了OCoF的基态四重态是能量较低的结构外，OMF和OMF都具有高自旋基态。M - O伸缩频率在键角、M - O和M - F伸缩的耦合以及氧上的自旋量方面是计算方法的一个敏感度量。基于CAS轨道的键合分析表明，在M = Cr之后，许多结构具有多参考特征。根据CASPT2结果给出了金属的氧化态。报告了OMF和OMF的生成热。
