Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective

doi:10.1039/c5dt04540a

	Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective
	Lan, JH; Wu, QY; Shi WQ(石伟群); Chai ZF(柴之芳); Cheng ZP(程仲平); Wang CZ(王聪芝); Lan JH(蓝建慧); Wu QY(吴群燕); Shi, WQ; Gibson, JK
刊名	DALTON TRANSACTIONS
	2016
卷号	45 期号:7 页码:3102
DOI	10.1039/c5dt04540a
通讯作者	石伟群
英文摘要	Recently, 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.
语种	英语
WOS记录号	WOS:000370165300042
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/261057]
专题	高能物理研究所_院士高能物理研究所_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,Wu, QY,Shi WQ,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.
APA	Lan, JH.,Wu, QY.,石伟群.,柴之芳.,程仲平.,...&Wang, CZ.(2016).Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective.DALTON TRANSACTIONS,45(7),3102.
MLA	Lan, JH,et al."Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective".DALTON TRANSACTIONS 45.7(2016):3102.