Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Ordoñez, Osvaldo; Yu, Xiaojuan; Autschbach, Jochen; Hayton, Trevor W.

doi:10.1021/acs.inorgchem.1c01686

Cited by 20 publications

(49 citation statements)

References 63 publications

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“…= 202.7 ppm) with 38.9 ppm deshielding due to SO effects. A similar magnitude in SO deshielding was previously found for [Th(C 6 Cl 5 ) 5 ] − and [ThCl 3 (C 6 Cl 5 ) 3 ] 2– , which also exhibit comparable amounts of 5f involvement in their Th–C bonds . In contrast, much stronger SO-induced deshielding was found for [U(O)(CC-C 6 H 4 - p -R){N(SiMe 3 ) 2 } 3 ] .…”

Section: Resultssupporting

confidence: 78%

“…The calculated positive charges for the acetylide hydrogen atoms suggest that they are acidic, consistent with their observed reactivities (Schemes and ). Moreover, the greater covalency and increased 5f involvement observed for the uranium analogues are consistent with the expected periodic trends. − Unsurprisingly, however, the degree of 5f orbital participation in 1 and 6 is significantly less than that observed for the uranium(VI) acetylide series [U(O)(CC-C 6 H 4 - p -R){N(SiMe 3 ) 2 } 3 ], which exhibit 28–29% total uranium weight, with 60–62% 5f orbital participation in their U–C bonds.…”

Section: Resultssupporting

confidence: 71%

“…As seen in Table , the calculated chemical shifts are only weakly dependent on the tested functionals; for brevity, we focus on the PBE/SO-PBE results. This functional has previously provided reliable chemical shifts in actinide complexes. , The calculated α-carbon shift for complex 2 is 174.9 ppm (expt. = 176.1 ppm) and includes a 32.2 ppm deshielding contribution due to SO effects.…”

Section: Resultsmentioning

confidence: 99%

“…This functional has previously provided reliable chemical shifts in actinide complexes. 23,48 The calculated α-carbon shift for complex 2 is 174.9 ppm (expt. = 176.1 ppm) and includes a 32.2 ppm deshielding contribution due to SO effects.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures

Kent

Pauly

et al. 2021

Inorg. Chem.

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The reaction of [AnCl(NR2)3] (An = U or Th; R = SiMe3) with NaCCH and tetramethylethylenediamine (TMEDA) results in the formation of [An(CCH)(NR2)3] (1, An = U; 2, An = Th), which can be isolated in good yields after workup. Similarly, the reaction of 3 equiv of NaCCH and TMEDA with [AnCl(NR2)3] results in the formation of [Na(TMEDA)][An(CCH)2(NR2)3] (4, An = U; 5, An = Th), which can be isolated in fair yields after workup. The reaction of 1 with 2 equiv of KC8 and 1 equiv of 2.2.2-cryptand in tetrahydrofuran results in formation of the uranium(III) acetylide complex [K(2.2.2-cryptand)][U(CCH)(NR2)3] (3). Thermolysis of 1 or 2 results in formation of the bimetallic dicarbide complexes [{An(NR2)3}2(μ,η1:η1-C2)] (6, An = U; 7, An = Th), whereas the reaction of 1 with [Th{N(R)(SiMe2 CH2)}(NR2)2] results in the formation of [U(NR2)3(μ,η1:η1-C2)Th(NR2)3] (8). The 13C NMR chemical shifts of the α-acetylide carbon atoms in 2, 5, and 7 exhibit a characteristic spin–orbit-induced downfield shift, due to participation of the 5f orbitals in the Th–C bonds. Magnetism measurements demonstrate that 6 displays weak ferromagnetic coupling between the uranium(IV) centers (J = 1.78 cm–1).

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Section: Resultssupporting

confidence: 78%

Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures

Kent

Pauly

et al. 2021

Inorg. Chem.

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“…The U1–Cl1 distance in ( Cl2Ph PDP Ph )UO 2 (THF) is significantly longer than Cl → U dative interactions (3.006(4)–3.227 (3) Å) involving the ortho -Cl atoms of C 6 Cl 5 ligands in a pair of U(IV) complexes characterized by Hayton and co-workers. 99 Moreover, the solid-state structure of ( Cl2Ph PDP Ph )UO 2 (THF) is C 1 symmetric. This result is inconsistent with the NMR data, which indicates that the complex possesses C 2 v symmetry in the solution.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Pyridine Dipyrrolide Uranyl Complexes

et al. 2022

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The first actinide complexes of the pyridine dipyrrolide (PDP) ligand class, ( Mes PDP Ph )UO 2 (THF) and ( Cl2Ph PDP Ph )UO 2 (THF), are reported as the U VI uranyl adducts of the bulky aryl substituted pincers ( Mes PDP Ph ) 2– and ( Cl2Ph PDP Ph ) 2– (derived from 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1 H -pyrrol-2-yl)pyridine (H 2 Mes PDP Ph , Mes = 2,4,6-trimethylphenyl), and 2,6-bis(5-(2,6-dichlorophenyl)-3-phenyl-1 H -pyrrol-2-yl)pyridine (H 2 Cl2Ph PDP Ph , Cl 2 Ph = 2,6-dichlorophenyl), respectively). Following the in situ deprotonation of the proligand with lithium hexamethyldisilazide to generate the corresponding dilithium salts (e.g., Li 2 Ar PDP Ph , Ar = Mes of Cl 2 Ph), salt metathesis with [UO 2 Cl 2 (THF) 2 ] 2 afforded both compounds in moderate yields. The characterization of each species has been undertaken by a combination of solid- and solution-state methods, including combustion analysis, infrared, electronic absorption, and NMR spectroscopies. In both complexes, single-crystal X-ray diffraction has revealed a distorted octahedral geometry in the solid state, enforced by the bite angle of the rigid meridional ( Ar PDP Ph ) 2– pincer ligand. The electrochemical analysis of both compounds by cyclic voltammetry in tetrahydrofuran (THF) reveals rich redox profiles, including events assigned as U VI /U V redox couples. A time-dependent density functional theory study has been performed on ( Mes PDP Ph )UO 2 (THF) and provides insight into the nature of the transitions that comprise its electronic absorption spectrum.

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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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Homoleptic Perchlorophenyl “Ate” Complexes of Thorium(IV) and Uranium(IV)

Cited by 20 publications

References 63 publications

Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures

Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures

Synthesis and Characterization of Pyridine Dipyrrolide Uranyl Complexes

Organouranium Chemistry

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