Tetrahalide Complexes of the [U(NR)<sub>2</sub>]<sup>2+</sup> Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

Spencer, Liam; Yang, Ping; Minasian, Stefan G.; Jilek, Robert E.; Batista, Enrique R.; Boland, Kevin S.; Boncella, James M.; Conradson, Steven D.; Clark, David L.; Hayton, Trevor W.; Kozimor, Stosh A.; Martin, Richard L.; MacInnes, Molly M.; Olson, Angela C.; Scott, Brian L.; Shuh, David K.; Wilkerson, Marianne P.

doi:10.1021/ja310575j

Cited by 92 publications

(75 citation statements)

References 89 publications

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“…This desire stems not only from a need to develop our knowledge and understanding of actinide bonding at a fundamental level45678, but also because of potential applications in nuclear waste clean-up which might utilize extraction methods that exploit covalency differences in metal-ligand bonding9. Because actinide-ligand multiple bonds arguably contain the greatest opportunities to probe covalency101112, in recent years in addition to numerous oxo complexes12 there has been intensive progress in uranium-carbene13141516171819, -imido202122232425262728, -nitride29303132, -phosphinidene/-arsinidene/-arsenido33343536 and -chalcogenido (S, Se, Te) chemistry37383940.…”

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confidence: 99%

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

et al. 2016

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Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.

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confidence: 99%

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

et al. 2016

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“…In recent years, many novel uranium molecules have become available, some accompanied by detailed spectroscopic and magnetic data45678910. However, a comprehensive electronic structure picture has thus far been limited to a few isolated studies of highly symmetric species56781112.…”

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confidence: 99%

“…However, a comprehensive electronic structure picture has thus far been limited to a few isolated studies of highly symmetric species56781112. In this regard, 5 f 1 complexes are appealing1112 because inter-electronic repulsion is absent.…”

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confidence: 99%

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

et al. 2016

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Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin–orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spin–orbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spin–orbit coupled states, and show measurement of UV···UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field.

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“…Despite the developed nature of uranium–ligand multiple bond chemistry1234—that is burgeoning due to a pressing need to improve our fundamental understanding of the chemical bonding of actinide (An) elements56789 and how this might impact reactivity and nuclear waste clean-up1011—the chemistry of other An–ligand multiple bonds, aside from actinyls, AnO 2 n+ (ref. 12), remains extremely rare13.…”

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Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

et al. 2017

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Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

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Tetrahalide Complexes of the [U(NR)₂]²⁺ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

Cited by 92 publications

References 89 publications

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

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Tetrahalide Complexes of the [U(NR)2]2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

Cited by 92 publications

References 89 publications

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

Contact Info

Product

Resources

About

Tetrahalide Complexes of the [U(NR)₂]²⁺ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy