Side-On OMoF2(eta(2)-SO) and OWF2(eta(2)-SO) Complexes Featuring Peroxo-Like Sulfur Monoxide Ligand

doi:10.1021/acs.inorgchem.9b02766

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 OMoF2(eta(2)-SO) and OWF2(eta(2)-SO) Complexes Featuring Peroxo-Like Sulfur Monoxide Ligand
	Wei, R ; Chen, XT ; Gong, Y
刊名	INORGANIC CHEMISTRY
	2019
卷号	58 期号:22 页码:15652-15658
关键词	INFRARED-SPECTRA COORDINATION OXIDES ATOMS MO CR METHYLIDENE OXIDATION 2ND
ISSN号	0020-1669
DOI	10.1021/acs.inorgchem.9b02766
文献子类	期刊论文
英文摘要	Peroxo-like sulfur monoxide complexes of molybdenum and tungsten oxyfluorides [OMF2(eta(2)-SO)] were prepared via the reactions of molybdenum and tungsten atoms and SO2F2 in cryogenic matrixes. On the basis of the infrared spectra and density functional theory calculations, the SO ligand is bound to the metal center in a sideon fashion, and both complexes possess closed shell singlet ground states. The experimental S-O stretching frequencies of OMoF2(eta(2)-SO) and OWF2(eta(2)-SO) are much lower than those of SO - but close to that of singlet SO2, indicating that the SO ligand should be considered as SO2-. This is consistent with the rather long S-O bond length in comparison to that of the ONbF(2(eta)2 -SO) and OTaF2(eta(2)-SO) complexes with SO - ligand. Bonding analysis results reveal that the pi* (3 pi) orbitals of the triplet SO molecule are both doubly occupied in OMoF2(eta(2)-SO) and OVVF2(eta(2)-SO) due to the two-electron transfer from metal to SO. End-on isomers with M-OS or M-SO geometries were also predicted to be stable, but all of them are higher in energy than the side-on complexes, and the calculated frequencies are inconsistent with the experimental values. Comparisons in bond lengths, vibrational frequencies, and natural charges between the OMF2(eta(2)-SO) and OMF2(eta(2)-SO) complexes (M = Mo, W, Nb, Ta) further confirm the peroxo-like character of the SO ligand in OMF2(eta(2)-SO) and OWF2(eta(2)-SO).
语种	英语
内容类型	期刊论文
源URL	[http://ir.sinap.ac.cn/handle/331007/32199]
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, Dept Radiochem, Shanghai Inst Appl Phys, 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 OMoF2(eta(2)-SO) and OWF2(eta(2)-SO) Complexes Featuring Peroxo-Like Sulfur Monoxide Ligand[J]. INORGANIC CHEMISTRY,2019,58(22):15652-15658.
APA	Wei, R,Chen, XT,&Gong, Y.(2019).Side-On OMoF2(eta(2)-SO) and OWF2(eta(2)-SO) Complexes Featuring Peroxo-Like Sulfur Monoxide Ligand.INORGANIC CHEMISTRY,58(22),15652-15658.
MLA	Wei, R,et al."Side-On OMoF2(eta(2)-SO) and OWF2(eta(2)-SO) Complexes Featuring Peroxo-Like Sulfur Monoxide Ligand".INORGANIC CHEMISTRY 58.22(2019):15652-15658.