Synthesis and Characterization of a Neutral U(II) Arene Sandwich Complex

Billow, Brennan S.; Livesay, Brooke N.; Mokhtarzadeh, Charles C.; McCracken, John; Shores, Matthew P.; Boncella, James M.; Odom, Aaron L.

doi:10.1021/jacs.8b10888

Cited by 94 publications

(129 citation statements)

References 22 publications

(39 reference statements)

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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 Reactionssupporting

confidence: 87%

“…[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%

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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 Reactionssupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…[11][12][13][14][15][16][17][18][19] When an ew oxidation state is identified, one of the characteristics to be defined is the redox potential by which it is formed. [11][12][13][14][15][16][17][18][19] When an ew oxidation state is identified, one of the characteristics to be defined is the redox potential by which it is formed.…”

mentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10] Additionally,e xamples of these new ions in other ligand environments have also been reported. [11][12][13][14][15][16][17][18][19] When an ew oxidation state is identified, one of the characteristics to be defined is the redox potential by which it is formed. Electrochemical analysiso ft he oxidation states of the rare-earth metalsa nd the actinides has historically been challenging due to the high reactivity and oxophilicity of these species.…”

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confidence: 99%

Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy

Moehring

Evans

2020

Chemistry A European J

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The possibility that the relative reactivity of complexes of actinidem etalsi nt he + 2a nd + 3o xidation states could be investigated by examining reactions between An III and An II species of Th and Uw ithr are-earth metal reagents that provide EPR confirmation of electron transfer reactivity has been explored. 2 ). 1À ,r espectively, which wereidentified by EPR spectroscopy.The reverse reactions also occur which indicates that the reduction potentials are similar.[ Cp'' 3 La II ] 1À reduces Cp' 3 Y III and the reverse Y II /La III combination also occurs.I nb othc ases, the reactions generate EPR spectra indicative of multiple species in the mixtures of La II and Y II ,w hich is consistent with ligand exchange and demonstrates that numeroush eteroleptic complexes of these Ln II ions exist.Ar ecent development in rare-earth and actinide chemistry is the discovery that the + 2oxidation state is availableincrystallographically characterizable molecular speciesf or many more metals than was previously expected. Specifically, the first crystallographically-characterizable

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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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Synthesis and Characterization of a Neutral U(II) Arene Sandwich Complex

Cited by 94 publications

References 22 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

Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy

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

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