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Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective
Wu QY(吴群燕); Lan JH(蓝建慧); Wang CZ(王聪芝); Cheng ZP(程仲平); Chai ZF(柴之芳); Shi WQ(石伟群); Wu, QY; Lan, JH; Wang, CZ; Cheng, ZP; Chai, ZF; Gibson, JK; Shi, WQ
2016
Source PublicationDALTON TRANSACTIONS
ISSN1477-9226
EISSN1477-9234
Volume45Issue:7Pages:3102-3110
Corresponding Author石伟群
SubtypeArticle
AbstractRecently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La-Nd, Sm-Lu) and actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent actinide complexes, a series of divalent actinide species, [AnCp'3](-) (An=Th-Am, Cp' = [eta(5)-C5H4(SiMe3)](-)) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the + 2 actinide ions and Cp' ligands. The ground state electron configurations for the [AnCp'3](-) species are [ThCp'3](-) 6d(2), [PaCp'3](-) 5f(2)6d(1), [UCp'3](-) 5f(3)6d(1), [NpCp'3](-) 5f(5), [PuCp'3](-) 5f (,) and [AmCp'3](-) 5f(7), respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp'3. [AnCp'3](-) should become increasingly facile across the actinide series from Th to Am, in accord with the known An(III/II) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.
DOI10.1039/c5dt04540a
WOS KeywordDENSITY-FUNCTIONAL THEORY ; CRYSTALLINE MOLECULAR-COMPLEX ; OXIDATION-STATE ; BASIS-SETS ; CORRELATION-ENERGY ; ELECTRON-DENSITY ; TH-CM ; LANTHANIDE ; BONDS ; URANIUM
Indexed BySCI
Language英语
WOS IDWOS:000370165300042
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Document Type期刊论文
Identifierhttp://ir.ihep.ac.cn/handle/311005/261057
Collection院士
多学科研究中心
Affiliation中国科学院高能物理研究所
Recommended Citation
GB/T 7714
Wu QY,Lan JH,Wang CZ,et al. Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective[J]. DALTON TRANSACTIONS,2016,45(7):3102-3110.
APA 吴群燕.,蓝建慧.,王聪芝.,程仲平.,柴之芳.,...&Shi, WQ.(2016).Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective.DALTON TRANSACTIONS,45(7),3102-3110.
MLA 吴群燕,et al."Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective".DALTON TRANSACTIONS 45.7(2016):3102-3110.
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