Organometallic Actinide Complexes with Novel Oxidation States and Ligand Types

Hayton, Trevor W.; Kaltsoyannis, Nikolas

doi:10.1002/9781119115557.ch4

Cited by 13 publications

(11 citation statements)

References 231 publications

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“…65 These bonding models are widely used for the assessment of bonding trends in organometallic complexes of f elements. 66 − 78 …”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical Study of Actinide Complexes with Macropa

Kovács

2020

ACS Omega

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The complex formation of actinium (Ac 3+ ) and californium (Cf 3+ ) ions with macropa (a promising ligand for medical applications, e.g., in targeted α therapy) has been studied by means of density functional theory (DFT) calculations. This work is focused on the structural and bonding properties, the latter on the basis of charge transfer data and topological properties of the electron density distribution. The effect of water solvent on the energetics has been investigated using the SMD model. A comparative analysis with the related properties of two representative lanthanide (La, Lu) complexes has been performed.

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“…65 These bonding models are widely used for the assessment of bonding trends in organometallic complexes of f elements. 66 − 78 …”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical Study of Actinide Complexes with Macropa

Kovács

2020

ACS Omega

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“…However, despite the many precedents of inverse-sandwich diuranium arene complexes, and the close analogy between thorium and uranium, − there is no example of an inverse-sandwich dithorium arene complex. Even thorium complexes of reduced arenes are rare: only three structurally characterized thorium reduced naphthalene complexes, in which Th(IV) was bound to a distorted naphthalene dianion in an η 4 -mode, were reported by Gambarotta et al − …”

mentioning

confidence: 99%

Arene-Bridged Dithorium Complexes: Inverse Sandwiches Supported by a δ Bonding Interaction

Liang

Deng

et al. 2020

J. Am. Chem. Soc.

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A series of arene-bridged dithorium complexes was synthesized via the reduction by potassium graphite of a Th(IV) precursor in the presence of arenes. All these compounds adopt an inverse-sandwich structure, with the arene bridging two thorium centers in a μ-η 6 ,η 6 -mode. Structural and spectroscopic data support the assignment of two Th(IV) ions and an arene tetraanion, which is an aromatic structure according to Huckel's rule. Arene exchange reactions revealed that the stability of the corresponding compounds follows the series naphthalene ≪ toluene < benzene ≈ biphenyl. Reactivity studies showed that they function as fourelectron reductants capable to reduce anthracene, cyclooctatetraene, alkynes, and azobenzene, while a mononuclear thorium anthracene complex could reduce benzene. Density functional theory calculations unveiled that the bonding interactions consist of δ bonds between thorium 6d and 5f orbitals and arene π* orbitals, showing a significant covalent character, able to stabilize highly reduced arene ligands.

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“…The bonding properties of the complexes were analyzed using the extended transition state (ETS) energy decomposition [15,18] and the quantum theory of atoms in molecules (QTAIM) models [16]. These theoretical models have been successfully applied in numerous studies of bonding trends in organometallic complexes [14,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34].…”

Section: Bonding Analysismentioning

confidence: 99%

Tris-{Hydridotris(1-pyrazolyl)borato}lanthanide Complexes: Synthesis, Spectroscopy, Crystal Structure and Bonding Properties

et al. 2021

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Complexes of trivalent lanthanides (Ln) with the hydridotris(1-pyrazolyl)borato (Tp) ligand Ln[η3-HB(N2C3H3)3]3 (LnTp3) were subjected to a joint experimental–theoretical analysis. X-ray diffraction experiments have been performed on CeTp3, NdTp3, SmTp3, GdTp3, and TbTp3 in the nine-fold coordination and on DyTp3, HoTp3, ErTp3, TmTp3, YbTp3, and LuTp3 in the eight-fold coordination form. Density functional theory (DFT) calculations were carried out for all 15 LnTp3 complexes. They extended the X-ray diffraction data available on the LnTp3 compounds and facilitated a straightforward interpretation of trends in the structural parameters. As a result of the joint analysis, significant steric strain in the equatorial coordination sites of the nine-coordinate structures was recognized. Trends in the bonding properties were elucidated by energy decomposition and quantum theory of atoms in molecules (QTAIM) analysis of the electron density distribution. These results revealed the major electrostatic character of the Ln…Tp bonding and fine variation of charge transfer effects across the Ln row.

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Organometallic Actinide Complexes with Novel Oxidation States and Ligand Types

Cited by 13 publications

References 231 publications

Theoretical Study of Actinide Complexes with Macropa

Theoretical Study of Actinide Complexes with Macropa

Arene-Bridged Dithorium Complexes: Inverse Sandwiches Supported by a δ Bonding Interaction

Tris-{Hydridotris(1-pyrazolyl)borato}lanthanide Complexes: Synthesis, Spectroscopy, Crystal Structure and Bonding Properties

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