Synthesis and structures of dioxouranium complexes with 2-pyridineformamide thiosemicarbazones

García‐Santos, Isabel; Abram, Ulrich

doi:10.1016/j.inoche.2004.01.005

Cited by 18 publications

(5 citation statements)

References 6 publications

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“…The Cambridge Structural Database contains only one entry of a uranyl compound with a uranium–phosphorus bond and less than 60 with U–S bonds, while a larger variety of complexes with soft or mixed hard/soft donor ligands is known for uranium in the oxidation state +4 or +3 . This includes, e.g., chalcogenocarbamates, , thiosemicarbazones, , imidodiphosphinochalcogenides, and bis(thiophosphinoyl)methanediides. − …”

Section: Introductionmentioning

confidence: 99%

Uranyl Complexes with Aroylbis(N,N-dialkylthioureas)

et al. 2018

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The reaction of isophthaloylbis( N, N-diethylthiourea), HL, with UO(CHCOO)·2HO and NEt as a supporting base gives a tetranuclear, anionic complex of the composition [{UO(L)}(OAc)], in which the uranyl ions are S, O-chelate bonded. Each two of them are additionally linked by an acetato ligand. Similar reactions of various uranyl starting materials (uranyl acetate, uranyl nitrate, (NBu)[UOCl]) with corresponding pyridine-centered ligands (pyridine-2,6-dicarbonylbis( N, N-dialkylthioureas), HL) yield mononuclear, neutral compounds, in which the thiourea derivatives are coordinated as S, N, N, N, S-five-dentate chelators. The equatorial coordination spheres of the formed hexagonal bipyramidal complexes [UO(L)(solv)] are completed by solvent ligands (HO, MeOH, or DMF). Attempted reactions without a supporting base result in decomposition of the organic ligands and the formation of hexanuclear uranyl complexes with pyridine-2,6-dicarboxylato ligands, while the use of an excess of base results in condensation and the formation of dinuclear [{UO(L)(μ-OMe)}] complexes. A stable complex of the composition [UO(L)] results from reactions of common uranyl starting materials with 2,2'-bipyridine-6,6'-dicarbonylbis( N, N-diethylthiourea) (HL). The equatorial coordination sphere of the neutral, hexagonal bipyramidal complex is occupied by an SNS donor atom set, which is provided by the hexadentate organic ligand. While the uranium complexes with {L} and {L} are labile and rapidly decompose in acidic solutions, [UO(L)] is stable over a wide pH range, and the ligand readily extracts uranyl ions from aqueous solutions into organic solvents.

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Section: Introductionmentioning

confidence: 99%

Uranyl Complexes with Aroylbis(N,N-dialkylthioureas)

et al. 2018

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“…Additionally, the bond distances change with a shortening of the U−S bond to 2.739 Å (U1−S1)/2.752 Å (U1−S2) and an elongation of the U−N bond to 2.535 Å (U1−N1)/2.569 Å (U1−N4). Only five other thiosemicarbazone complexes with uranyl(VI) are known with this five‐membered coordination motif [21,22,31] . Thus, this is the first uranium(IV) compound showing this five membered ring and a specific change of the coordination motif by just the methylation of an NH 2 group.…”

Section: Introductionmentioning

confidence: 88%

“…Only five other thiosemicarbazone complexes with uranyl(VI) are known with this five-membered coordination motif. [21,22,31] Thus, this is the first uranium(IV) compound showing this five membered ring and a specific change of the coordination motif by just the methylation of an NH 2 group.…”

Section: Introductionmentioning

confidence: 98%

“…Aerosol assisted CVD was carried out with homoleptic zinc(II) thiosemicarbazones and heteroleptic tribenzyltin(IV)chloride thiosemicarbazones of the type Bz 3 SnCl(TSC) to deposit ZnS and SnS thin films, respectively. [17,18] Remarkably, among only three heteroleptic Ln complexes [19,20] and four uranyl compounds, [21][22][23] no research has been carried out on lanthanides and actinides with such ligands. Herein we present the first thiosemicarbazone complexes of uranium(IV).…”

Section: Introductionmentioning

confidence: 99%

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Thiosemicarbazone Complexes of Uranium(IV)

et al. 2021

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The first homoleptic thiosemicarbazone complexes of uranium were isolated by reacting uranium tetrachloride in a salt metathesis or acid-base reaction with four equivalents of Na(BzTSC) or H(BzTSC) (BzTSC = benzylthiosemicarbazone), carrying a non-methylated (L1), monomethylated (L2) or dimethylated (L3) terminal amino group, in moderate yields. [U-(BzTSCNH 2) 4 ] (1), [U(BzTSCNH(CH 3)) 4 ] (2) and [U(BzTSCN(CH 3) 2) 4 ] (3) show a remarkable stability towards air, with oxidation potentials in THF between + 0.43 and + 0.53 V and reduction potentials between À 2.53 and À 2.67 V vs. ferrocene/ferrocenium. The simple methylation of the terminal amino group of the ligand allows for controlled changes in the coordination environments of the complexes. Thermogravimetric analyses indicate that the complexes are stable up to 155°C.

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“…It has been experimentally observed that an auxiliary N-donor ligand can enhance the lanthanide–actinide separation with a S-donor ligand . Only a handful of complexes for low-valent actinides with a conjugated N,S-donor ligand were reported, such as for Th(IV), , U(IV), − Pu(III), and Am(III) . However, these N,S-donor ligands may possess redox-active properties, where N and/or S can be of radical character in metal complexes depending on the specific ligand structure and the oxidation state of the metal center.…”

Section: Introductionmentioning

confidence: 99%

Unusual Actinyl Complexes with a Redox-Active N,S-Donor Ligand

Gong

Batista

et al. 2023

Inorg. Chem.

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Understanding the fundamental chemistry of soft N,S-donor ligands with actinides across the series is critical for separation science toward sustainable nuclear energy. This task is particularly challenging when the ligands are redox active. We herein report a series of actinyl complexes with a N,S-donor redox-active ligand that stabilizes different oxidation states across the actinide series. These complexes are isolated and characterized in the gas phase, along with high-level electronic structure studies. The redox-active N,S-donor ligand in the products, C5H4NS, acts as a monoanion in [UVIO2(C5H4NS–)]+ but as a neutral radical with unpaired electrons localized on the sulfur atom in [NpVO2(C5H4NS•)]+ and [PuVO2(C5H4NS•)]+, resulting in different oxidation states for uranium and transuranic elements. This is rationalized by considering the relative energy levels of actinyl(VI) 5f orbitals and S 3p lone pair orbitals of the C5H4NS– ligand and the cooperativity between An–N and An–S bonds that provides additional stability for the transuranic elements.

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Synthesis and structures of dioxouranium complexes with 2-pyridineformamide thiosemicarbazones

Cited by 18 publications

References 6 publications

Uranyl Complexes with Aroylbis(N,N-dialkylthioureas)

Uranyl Complexes with Aroylbis(N,N-dialkylthioureas)

Thiosemicarbazone Complexes of Uranium(IV)

Unusual Actinyl Complexes with a Redox-Active N,S-Donor Ligand

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