Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides

doi:10.1021/acs.inorgchem.8b03411

CORC > 上海应用物理研究所 > 中国科学院上海应用物理研究所 > 中科院上海应用物理研究所2011-2017年

	Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides
	Wei, R ; Chen, XT ; Gong, Y
刊名	INORGANIC CHEMISTRY
	2019
卷号	58 期号:6 页码:3807—3814
关键词	GAUSSIAN-BASIS SETS INFRARED-SPECTRA THEORETICAL INVESTIGATIONS MOLECULAR CALCULATIONS ATOM REACTIONS TRIPLE BONDS METAL ATOM COORDINATION ACTIVATION TITANIUM
ISSN号	0020-1669
DOI	10.1021/acs.inorgchem.8b03411
文献子类	期刊论文
英文摘要	Side-on sulfur monoxide complexes of tantalum, niobium, and vanadium oxyfluorides OMF2(eta(2)-S0) were prepared via the reactions of metal atoms and SO2F2 upon UV-vis irradiation in a cryogenic matrix. The product structures were identified by the characteristic infrared absorptions and isotopic frequency ratios of terminal M-O, F-M-F, and M-(SO) stretches, which were further supported by density functional theory calculations at the B3LYP level. All of the three complexes were predicted to have doublet ground states with the S-O bond nearly perpendicular to the terminal metal-oxygen bond. Although end-on bonded isomers with either M-OS or M-SO geometry are stable as well, they are higher in energy than the side-on isomers, and their vibrational frequencies do not match the experimental values. For the OMF2(eta(2)-S0) complexes, the S-O bond length approaches that of SO-, but it is longer than that of neutral SO due to the electron transfer from the metal d orbital to the in-plane 7 pi orbital of SO. The metal-SO bonding in the side-on complex is mainly ionic, but covalent interactions play some role between the two parts. On the basis of the calculation results, the OMF2(r72-S0) complexes can be considered as (OMF2) (SO)(-) in which the unpaired electron is mainly located in the out-of plane pi orbital of SO. In addition to the complexes containing SO ligand, a series of other stable isomers were obtained by the B3LYP calculations, and they were proposed as intermediates involved in the formation of the OMF2(7/2-S0) products via fluorine and oxygen transfer reactions between metal atoms and SO2F2 under UV-vis irradiation.
语种	英语
内容类型	期刊论文
源URL	[http://ir.sinap.ac.cn/handle/331007/31812]
专题	上海应用物理研究所_中科院上海应用物理研究所2011-2017年
作者单位	1.Chinese Acad Sci, Shanghai Inst Appl Phys, Dept Radiochem, Shanghai 201800, Peoples R China; 2.Univ Chinese Acad Sci, Sch Nucl Sci & Technol, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Wei, R,Chen, XT,Gong, Y. Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides[J]. INORGANIC CHEMISTRY,2019,58(6):3807—3814.
APA	Wei, R,Chen, XT,&Gong, Y.(2019).Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides.INORGANIC CHEMISTRY,58(6),3807—3814.
MLA	Wei, R,et al."Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides".INORGANIC CHEMISTRY 58.6(2019):3807—3814.