Synthesis and Utility of Neptunium(III) Hydrocarbyl Complex

Myers, Alexander J.; Tarlton, Michael L.; Kelley, Steven P.; Lukens, Wayne W.; Walensky, Justin R.

doi:10.1002/ange.201906324

Cited by 4 publications

(3 citation statements)

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“…19 In addition to neptunium complexes bearing cyclopentadienyl ligands, [20][21][22] η 6 -arene complexes and hydrocarbyl-coordinated Np 4+ centers have also been described. [23][24][25] These systems have set the foundations of organoneptunium chemistry and analysis of its chemical bonds. Investigating novel coordination motifs in organoactinide complexes may provide further understanding of f-orbital participation in neptuniumligand bonding interactions.…”

Section: Introductionmentioning

confidence: 99%

Employing a template synthesis to access diastereopure Np(iv) and U(iv) complexes and analysis of their 5f orbitals in bonding

Carpenter,

Beltrán-Leiva,

Sharma

et al. 2024

Inorg. Chem. Front.

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Section: Introductionmentioning

confidence: 99%

Employing a template synthesis to access diastereopure Np(iv) and U(iv) complexes and analysis of their 5f orbitals in bonding

Carpenter,

Beltrán-Leiva,

Sharma

et al. 2024

Inorg. Chem. Front.

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“…atmosphere. [NpCl4(DME)2]17 and Np[η4 -Me2NC(H)C6H5]3172 were synthesized as previously described. Benzoyl peroxide was dried over magnesium sulfate before use.2,6-di-tert-butylphenol was recrystallized out of pentane and dried before use.…”

mentioning

confidence: 99%

“…Np(III) hydrocarbyl complex, Np[η4 -Me2NC(H)C6H5]3,172 and its ability to produce other Np(III) complexes through protonolysis reactions. Here, we demonstrate that Np[η 4 -…”

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confidence: 99%

Synthesis and reactivity of low-valent uranium and neptunium complexes

Myers¹

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Chapter 1 reports the synthesis and characterization of U(IV) and Np(IV) selenium bis(phenolate) complexes. The reaction of the U(IV) complex with half an equivalent of p-benzoquinone results in the formation of a U(V)--U(V) species with a bridging reduced quinone. This represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex. In Chapters 2 and 3 the synthesis and characterization of a rare U(III) hydrocarbyl complex, U[[eta]4-Me2NC(H)C6H5]3, and the first structurally characterized transuranic hydrocarbyl complex, Np[[eta]4-Me2NC(H)C6H5]3, complex, has been generated with four equivalents of the K[Me2NC(H)C6H5] ligand. In the analogous Th(IV) reaction, C-H bond activation of a methyl group of one dimethylamine was observed yielding Th[[eta]4-Me2NC(H)C6H5]2[[eta]5-(CH2)MeNC(H)C6H5] with a dianionic DMBA ligand. The utility of these complexes as starting materials has been analyzed using a bulky dithiocarboxylate ligand to yield tetravalent actinide species for U and Th but Np maintains the trivalent oxidation state. Chapter 4 describes the on-going synthesis and reactivity of Np(OAr)3 (Ar = 2,6-di-tert-butylphenoxide) utilizing Np[[eta]4-Me2NC(H)C6H5]3 as a Np(III) starting material. The coordination and oxidation chemistry is explored with [nBu4N]N3, (C6H5CO)2O2 and Ph2S2 resulting in a bridged Np(III)/Np(III) azide complex with an outer sphere nBu4N and Np(IV) species, respectively.

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Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization

Fichter

Kaufmann

Kaden

et al. 2020

Chemistry A European J

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The synthesis of a tetravalent neptunium amidinate [NpCl(( S )‐PEBA) 3 ] ( 1 ) (( S )‐PEBA=( S , S )‐ N , N′ ‐bis‐(1‐phenylethyl)‐benzamidinate) is reported. This complex represents the first structurally characterized enantiopure transuranic compound. Reactivity studies with halide/pseudohalides yielding [NpX(( S )‐PEBA) 3 ] (X=F ( 2 ), Br ( 3 ), N 3 ( 4 )) have shown that the chirality‐at‐metal is preserved for all compounds in the solid state. Furthermore, they represent an unprecedented example of a structurally characterized metal–organic Np complex featuring a Np−Br ( 3 ) bond. In addition, 4 is the only reported tetravalent transuranic azide. All compounds were additionally characterized in solution using para ‐magnetic NMR spectroscopy showing an expected C 3 ‐symmetry at low temperatures.

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Synthesis and Utility of Neptunium(III) Hydrocarbyl Complex

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 4 publications

References 73 publications

Employing a template synthesis to access diastereopure Np(iv) and U(iv) complexes and analysis of their 5f orbitals in bonding

Employing a template synthesis to access diastereopure Np(iv) and U(iv) complexes and analysis of their 5f orbitals in bonding

Synthesis and reactivity of low-valent uranium and neptunium complexes

Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization

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