Fluoroborylene Complexes FBMF2 (M = Sc, Y, La, Ce): Matrix Infrared Spectra and Quantum Chemical Calculations
Fluoroborylene Complexes FBMF2 (M = Sc, Y, La, Ce): Matrix Infrared Spectra and Quantum Chemical Calculations
复制标题
氟硼烯配合物 FBMF2（M = Sc、Y、La、Ce）：矩阵红外光谱和量子化学计算
DOI：
10.1021/acs.inorgchem.8b02801
复制
发表时间：
2019
影响因子：
4.6
通讯作者：
Wang Xuefeng
中科院分区：
文献类型：
--
作者：
Xu Bing;Li Li;Pu Zhen;Yu Wenjie;Li Wenjing;Wang Xuefeng
通过基体隔离红外光谱和量子化学计算，研究了4 K下激光烧蚀第3族过渡金属和铈原子与三氟化硼在过量固体氖中的反应。在惰性气体中捕获了氟代硼配合物FBMF 2（M = Sc，Y，La，Ce），并通过同位素取代进行了鉴定。通过DFT、NEVPT 2和CASSCF计算再现了FBMF 2的观测频率。从Sc到La，观察到的F-11B伸缩模在1391.9 cm-1（Sc），1370.8 cm-1（Y）和1337.1 cm-1（La）处观察到;然而，对于Ce，由于相对论效应，该模式移动到1340.8 cm-1。应用电子局域函数（ELF）分析和分子中原子理论（AIM）研究了FBMF 2分子中B-M键的性质，发现键级为1.5。
Laser-ablated group 3 transition metal and cerium atom reactions with boron trifluoride were explored in excess solid neon at 4 K through matrix isolation infrared spectroscopy and quantum chemical calculations. The fluoroborylene complexes FBMF2(M = Sc, Y, La, Ce) were trapped in inert gas and identified by the isotopic substitutions. The observed frequencies of FBMF2were reproduced by DFT, NEVPT2, and CASSCF calculations. From Sc to La, the observed F–11B stretching mode has been observed at 1391.9 cm–1(Sc), 1370.8 cm–1(Y), and 1337.1 cm–1(La); however, for Ce this mode shifts up to 1340.8 cm–1, which is due to relativistic effects. The electron localization function (ELF) analysis and the theory of atoms in molecules (AIM) were applied to investigate the character of the B–M bond in FBMF2molecules, which favors bond order 1.5.