Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

doi:10.1515/ract-2016-2615

	Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands
	Lan, JH; Chai, ZF; Gibson, JK; Shi, WQ; Wang CZ(王聪芝); Wu QY(吴群燕); Lan JH(蓝建慧); Chai ZF(柴之芳); Shi WQ(石伟群); Wang, CZ
刊名	RADIOCHIMICA ACTA
	2017
卷号	105 期号:1 页码:21-32
关键词	Density functional calculations binuclear uranium complexes halides cyanides cyclooctatetraene
ISSN号	0033-8230
DOI	10.1515/ract-2016-2615
文献子类	Article
英文摘要	Although the first organoactinide chloride Cp3UCl (Cp = eta(5)-C H-5(5)) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT)(2)U2Xn (COT = eta(8)-C8H8; X = F, Cl, CN; n = 2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT)(2)U2X (n), and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT)(2)U2Xn species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT)(2)U2X4 might be accessible through the known (COT)(2)U complex. The tetravalent derivatives (COT)(2)U2X4 are more energetically favorable than the trivalent (COT)(2)U2X2 analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.
WOS关键词	TRANSITION-METAL-COMPLEXES ; SEGMENTED CONTRACTION SCHEME ; EXCHANGE COUPLING-CONSTANTS ; PSEUDOPOTENTIAL BASIS-SETS ; DENSITY-FUNCTIONAL THEORY ; ELECTRONIC-STRUCTURES ; M(CO)(6) M=CR ; MAGNETIC-PROPERTIES ; CORRELATION-ENERGY ; APPROXIMATION
WOS研究方向	Chemistry ; Nuclear Science & Technology
语种	英语
WOS记录号	WOS:000394245800002
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/284954]
专题	高能物理研究所_多学科研究中心
作者单位	中国科学院高能物理研究所
推荐引用方式 GB/T 7714	Lan, JH,Chai, ZF,Gibson, JK,et al. Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands[J]. RADIOCHIMICA ACTA,2017,105(1):21-32.
APA	Lan, JH.,Chai, ZF.,Gibson, JK.,Shi, WQ.,王聪芝.,...&Wu, QY.(2017).Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands.RADIOCHIMICA ACTA,105(1),21-32.
MLA	Lan, JH,et al."Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands".RADIOCHIMICA ACTA 105.1(2017):21-32.