Metal-metal multiple bond in low-valent diuranium porphyrazines and its correlation with metal oxidation state: A relativistic DFT study

doi:10.1016/j.comptc.2017.03.011

	Metal-metal multiple bond in low-valent diuranium porphyrazines and its correlation with metal oxidation state: A relativistic DFT study
	Qu, N; Su, DM; Wu QY(吴群燕); Shi WQ(石伟群); Wu, QY; Shi, WQ; Pan, QJ
刊名	COMPUTATIONAL AND THEORETICAL CHEMISTRY
	2017
卷号	1108 页码:29-39
关键词	Diuranium diporphyrazine Metal-metal multiple bond Electronic structures QTAIM Relativistic DFT
ISSN号	2210-271X
DOI	10.1016/j.comptc.2017.03.011
文献子类	Article
英文摘要	To explore the uranium-uranium bonding nature, a ligated diuranium complex that could be experimentally possible would show features with no bridging ligand constraints (i.e. discrete or unsupported ligand), rigid ligand skeleton and suitable U-ligand bond. In this respect, we have designed and examined a series of diuranium diporphyrazines (U(2)(m)Pz(2), m = II, III and IV) using relativistic density functional theory. Optimizations on all possible electron-spin isomers find that the triplet, quintet and quintet states are energetically lowest for Um(2)Pz(2) (m = II, III and IV), respectively. They possess bond lengths of U-U at 2.37, 2.46 and 2.91 angstrom, bond orders of 3.48, 3.33 and 2.11, and stretching vibrational frequencies of 239, 172 and 108 cm(-1). Associated with the electronic-structure and QTAIM (quantum theory of atoms in molecules) analyses, a weak quadruple bond is suggested for the triplet state of U(2)(II)Pz(2), and the triple and double bonds for U(2)(III)Pz(2), and U(2)(IV)Pz2, respectively. It shows that the uranium oxidation state approximately correlates with the number of multiple bonds. (C) 2017 Elsevier B.V. All rights reserved.
电子版国际标准刊号	1872-7999
WOS关键词	ORDER REGULAR APPROXIMATION ; D-BLOCK ANALOGS ; ELECTRONIC-STRUCTURE ; POLYPYRROLIC MACROCYCLE ; OXO-FUNCTIONALIZATION ; MOLECULAR-STRUCTURE ; ACTINIDE COMPLEXES ; COVALENT RADII ; QUANTUM-THEORY ; SCHIFF-BASE
WOS研究方向	Chemistry
语种	英语
WOS记录号	WOS:000400717900005
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/285201]
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	Qu, N,Su, DM,Wu QY,et al. Metal-metal multiple bond in low-valent diuranium porphyrazines and its correlation with metal oxidation state: A relativistic DFT study[J]. COMPUTATIONAL AND THEORETICAL CHEMISTRY,2017,1108:29-39.
APA	Qu, N.,Su, DM.,吴群燕.,石伟群.,Wu, QY.,...&Pan, QJ.(2017).Metal-metal multiple bond in low-valent diuranium porphyrazines and its correlation with metal oxidation state: A relativistic DFT study.COMPUTATIONAL AND THEORETICAL CHEMISTRY,1108,29-39.
MLA	Qu, N,et al."Metal-metal multiple bond in low-valent diuranium porphyrazines and its correlation with metal oxidation state: A relativistic DFT study".COMPUTATIONAL AND THEORETICAL CHEMISTRY 1108(2017):29-39.