Isolation of a Perfectly Linear Uranium(II) Metallocene

Guo, Fu‐Sheng; Tsoureas, Nikolaos; Huang, Guo‐Zhang; Tong, Ming‐Liang; Mansikkamäki, Akseli; Layfield, Richard A.

doi:10.1002/anie.201912663

Cited by 79 publications

(76 citation statements)

References 45 publications

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“…13 When only considering the E 0 value, [U II L 2 ] would be synthetically accessible using similar approach in previous studies, as well as other actinide(II) complexes. [6][7][8][9][10][11][12][13][14][15][16][17][18][19] As seen in Fig. 2a, the trend obtained in the work is approximately the same as those of previous studies of Bratsch 27 and Nugent.…”

Section: Reduction Reactionsmentioning

confidence: 99%

“…Studies of the same group further had access to several U(II) complexes ligated by various substituted cyclopentadienyls (Cp) [7][8][9][10] and even a more electrondonating N(SiMe 3 ) 2 . 10 13 Interestingly, actinide(II) complexes such as Th, 14,15 Np [16][17][18] and Pu 19 have been synthetically accessible, most of which are accommodated by Cp-derived ligands. [14][15][16][17]19 It is worth noting that aforementioned U(II) complexes have some similarity and difference.…”

Section: Introductionmentioning

confidence: 99%

“…[14][15][16][17]19 It is worth noting that aforementioned U(II) complexes have some similarity and difference. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] Firstly, a lowtemperature synthetic route was developed by applying potassium graphite (KC 8 ) to reduce respective U(III) parent. Secondly, it is found that the stability of complex was partially contributed by d back-bonds between U and Ar/Cp.…”

Section: Introductionmentioning

confidence: 99%

“…For example, reports about reduction potentials of U(II) complexes are very rare, which may be restricted by experimental difficulties such as safe handling of high radioactivity, sample stability/scarcity and applicable solvent shortage. 5,[24][25][26][27] 13,25 In this regard, theoretical computation becomes appealing for it has been applied in many studies to successfully predict and conrm structural and redox properties of actinide-containing complexes. 22,[28][29][30][31][32][33][34] Ligand is the key to prepare stable actinide(II) complexes and explore their properties.…”

Section: Introductionmentioning

confidence: 99%

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Redox and structural properties of accessible actinide(ii) metallocalixarenes (Ac to Pu): a relativistic DFT study

et al. 2020

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Section: Reduction Reactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Redox and structural properties of accessible actinide(ii) metallocalixarenes (Ac to Pu): a relativistic DFT study

et al. 2020

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“…近年 [7] . 随后, 多个课题组先后合成几个二价铀配合物, 包括 Y•[UL E ] (L E ＝ [( Ad,Me ArOH) 3 mesitylene] 3-, Ad ＝ adamantyl) [8] 、 [U(NHAr iPr6 ) 2 ] (Ar iPr6 ＝ 2,6-(2,4,6-i Pr 3 C 6 H 2 ) 2 C 6 H 3 ) [9] 、 Y•[U{N(SiMe 3 ) 2 } 3 ] [10] 和[U(η 5 -C 5 i Pr 5 ) 2 ] [11] . 研究表明, 环戊二烯基(Cyclopentadienyl, Cp)配合物中铀的电子组态为 5f 3 6d 1 , 而芳香基(Arene, Ar)的为 5f 4 [7,10,[12][13][14] .…”

Section: 引言unclassified

Theoretical Probe for Tris(aryloxide)arene Complexed Low-valent Actinide Ions and Their Structural/Redox Properties

Yang¹,

Tian²,

Cai³

et al. 2020

Acta Chim. Sinica

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It is of great significance to identify new oxidation state of actinide, which will enrich actinide coordination chemistry and advance its exploration of chemical bond and reactivity. So far, uranium with ＋3～＋6 oxidation states has been widely recognized in complexes. Comparatively, isolated, crystallographically identified U(II) complexes remain rare. Inspired by the pioneering work of Evans and co-workers that Y•[U II (Cp') 3 ] (Y＝[K(2.2.2-cryptand)] ＋ , Cp'＝[C 5 H 4 SiMe 3 ]-) was structurally characterized, several uranium(II) complexes such as Y•[UL E ] (L E ＝[(Ad,Me ArO) 3 mesitylene] 3-, Ad＝ adamantyl), [U(NHAr iPr6) 2 ] (Ar iPr6 ＝2,6-(2,4,6-i Pr 3 C 6 H 2) 2 C 6 H 3), Y•[U{N(SiMe 3) 2 } 3 ] and [U(η 5-C 5 i Pr 5) 2 ] were synthetically accessible. Inspection finds that all these U(II) complexes were prepared in the same route, i.e., utilizing potassium graphite or potassium sphere to reduce respective U(III) parent at low temperature. Cyclopentadiene (Cp) and arene (Ar)-based ligands are involved. They are key to determine U(II) electron configuration, leading to 5f 3 6d 1 and 5f 4 , respectively. Moreover, δ(U-Ar) bonds play a significant role in stabilizing arene-ligated complexes. With the supporting of Cp-derived ligands, actinide(II) complexes were extended to Th, Np and Pu. Unfortunately, it is not the case for the arene ligands, even with massive efforts. Given the prevailing route that actinide(II) complex was synthesized by reducing its trivalent parent, the exploration of redox property will help to guide the synthesis of more novel U(II) and even other actinide(II) complexes. In this respect, theoretical computation based on accurate methodology is greatly appealing. Herein, relativistic density functional theory was exploited to investigate structural and redox properties of [AnL] z (An＝Ac～Pu; L＝[(Me,Me ArOH) 3 Ar] 3-; z＝0 and-1), where analogues of uranium complexes were experimentally known. It is found that the central arene moiety is redox-active for Ac and Th complexes in the reduction reaction, while the metal center is reduced for other complexes. So Ac and Th in reduced products still remain ＋3 oxidation states, whereas metals in others turn ＋2. The 5f n electronic configuration is unraveled for actinide of [AnL]-(An＝Pa～Pu), having 3～6 electrons, respectively. Calculated redox potential (E 0) increases from Ac to Pu in general, where U and Np show lower values than adjacent elements. A good correlation has been built between E 0 and Δ(An-C Ar /An-Ar cent)/electron affinity. In brief, the study is expected to provide theoretical support for the synthesis of novel arene-based actinide(II) complexes. Keywords δ(An-Ar)-type low-valent actinide complexes; tris(aryloxide)arene; electronic structure; redox reaction; relativistic density functional theory

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Organouranium Chemistry

Walter

2023

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Major research topics in organouranium chemistry during the calendar period 2014–2021 entail (i) the development of uranium complexes featuring the oxidation state +2, which has not been available in organic media until recently, (ii) the application of organouranium complexes in small molecule activation including multi‐electron processes, (iii) preparation of novel complexes featuring uranium‐element multiple bonds and uranium–metal bonds, (iv) new carbocycles in the coordination sphere of uranium, (v) the synthesis of well‐defined uranium metallacycles and their intrinsic reactivity, and (vi) applications in catalysis.

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Isolation of a Perfectly Linear Uranium(II) Metallocene

Cited by 79 publications

References 45 publications

Redox and structural properties of accessible actinide(ii) metallocalixarenes (Ac to Pu): a relativistic DFT study

Redox and structural properties of accessible actinide(ii) metallocalixarenes (Ac to Pu): a relativistic DFT study

Theoretical Probe for Tris(aryloxide)arene Complexed Low-valent Actinide Ions and Their Structural/Redox Properties

Organouranium Chemistry

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