Activation of Small Molecules by Molecular Uranium Complexes

Pierre, Henry S. La; Meyer, Karsten

doi:10.1002/9781118792797.ch05

Cited by 125 publications

(90 citation statements)

References 331 publications

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“…In recent years the study of actinide-ligand bonding has flourished due to a desire to better understand the nature of covalency in these linkages in terms of the extent of covalency and levels of metal-derived 7s-, 7p-, 6d- and 5f-orbital character123. 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.…”

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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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“…[4-6, 12, 13] The drive to understand the nature of bondingi nA n-complexes is not purely curiosity-driven, as there are many applications of An-ligand bondingi nc atalysis, [14][15][16] and small molecule activation. [17,18] The separation of actinides from spent nuclear fuel through complex formation remains an important field of research as well. [19] Following the discoveryo fu ranocene in 1968, [20] and thorocene in 1969, [21] the actinocene sandwich complexes of An with the ligand C 8 H 8 2À (cyclooctatatradienyl, COT) have taken their place among the most studied An complexes,b oth experimentally and theoretically,d ue to their interesting bonding features.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Analysis of Metal–Ligand Bonding in An(COT)₂ with An=Th, U in Their Ground‐ and Core‐Excited States

Ganguly

Sergentu

Autschbach

2020

Chemistry A European J

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Relativistic multireference ab initio wave function calculations with the restricted active space second-order perturbation theory (RASPT2) were performed on thorocene and uranocene to determine the actinide N 4,5 -edge and carbon K-edge X-ray absorption near-edge structure (XANES) intensities andt he metal-ligand orbitalm ixingi nt he ground state and core-excited states. Calculated spectrali ntensities show very good agreement with the experiments and therefore allow detailed and unambiguous assignment of the observed spectral features. f-type covalent bonding or antibonding interactions are observed for thorocene in the core-excited states, thoughn ot in the ground state. This is because the molecular orbital of f symmetry,w hich is the in-phasec ombination of the ligand L f and the Th 5f f orbitals, can be populated with electrons in core-excited states, whereas it is essentially unoccupied in the ground state. For uranocene, the XANES spectra do not reveal much information beyondm ultipletb roadening, despite the presence of distinct peaks in the spectra. Every core-excited peak is best characterized by its own set of bond orbitals, as the excited state covalency is clearly different from the ground state covalency.[a] Dr.

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“…Molecular actinide compounds can house electrons in 5f, 6d, 7p, and 7s orbitals, leading to patterns in chemical reactivity, 1 – 3 structural motifs 4 – 7 and magnetic properties 8 , 9 that are uncommon for metals in other parts of the periodic table. To account for this behaviour, it is necessary to examine how actinide-based electrons are perturbed by ligand field interactions while also considering the effects of strong spin–orbit coupling and significant electron–electron repulsion.…”

Section: Introductionmentioning

confidence: 99%

Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex

et al. 2018

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Activation of Small Molecules by Molecular Uranium Complexes

Cited by 125 publications

References 331 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

Ab Initio Analysis of Metal–Ligand Bonding in An(COT)₂ with An=Th, U in Their Ground‐ and Core‐Excited States

Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex

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Activation of Small Molecules by Molecular Uranium Complexes

Cited by 125 publications

References 331 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

Ab Initio Analysis of Metal–Ligand Bonding in An(COT)2 with An=Th, U in Their Ground‐ and Core‐Excited States

Chemical structure and bonding in a thorium(iii)–aluminum heterobimetallic complex

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Ab Initio Analysis of Metal–Ligand Bonding in An(COT)₂ with An=Th, U in Their Ground‐ and Core‐Excited States