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Actinide Series

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Thomas E. Albrecht-schmitt – One of the best experts on this subject based on the ideXlab platform.

  • Directed evolution of the periodic table: probing the electronic structure of late Actinides
    Dalton transactions (Cambridge England : 2003), 2017
    Co-Authors: Matthew L. Marsh, Thomas E. Albrecht-schmitt

    Abstract:

    Recent investigations of the coordination chemistry and physical properties of berkelium (Z = 97) and californium (Z = 98) have revealed fundamental differences between post-curium elements and lighter members of the Actinide Series. This review highlights these developments and chronicles key findings and concepts from the last half-century that have helped usher in a new understanding of the evolution of electronic structure in the periodic table.

  • Fleeting glimpse of an elusive element
    Nature, 2016
    Co-Authors: Thomas E. Albrecht-schmitt

    Abstract:

    A heroic effort to characterize the chemistry of actinium, a short-lived radioactive element, reveals surprising differences in behaviour compared with other elements in the Actinide Series.

  • Inorganic chemistry: Fleeting glimpse of an elusive element
    Nature, 2016
    Co-Authors: Thomas E. Albrecht-schmitt

    Abstract:

    A heroic effort to characterize the chemistry of actinium, a short-lived radioactive element, reveals surprising differences in behaviour compared with other elements in the Actinide Series.

Nikolas Kaltsoyannis – One of the best experts on this subject based on the ideXlab platform.

  • Quantum chemical topology and natural bond orbital analysis of M-O covalency in M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np).
    Physical chemistry chemical physics : PCCP, 2020
    Co-Authors: Victoria E. J. Berryman, Jacob J. Shephard, Tatsumi Ochiai, Amy N. Price, Polly L. Arnold, Simon Parsons, Nikolas Kaltsoyannis

    Abstract:

    Covalency is complex yet central to our understanding of chemical bonding, particularly in the Actinide Series. Here we assess covalency in a Series of isostructural d and f transition element compounds M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange–correlation covalency metric is evaluated for the first time for Actinides other than uranium, in order to assess its applicability in the 5f Series. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal–ligand bonding. Our range of metrics agree that the Actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early Actinide Series, Th stands apart from the other three elements considered, being consistently the least covalent.

  • Transuranic Computational Chemistry
    Chemistry (Weinheim an der Bergstrasse Germany), 2017
    Co-Authors: Nikolas Kaltsoyannis

    Abstract:

    Recent developments in the chemistry of the transuranic elements are surveyed, with particular emphasis on computational contributions. Examples are drawn from molecular coordination and organometallic chemistry, and from the study of extended solid systems. The role of the metal valence orbitals in covalent bonding is a particular focus, especially the consequences of the stabilization of the 5f orbitals as the Actinide Series is traversed. The fledgling chemistry of transuranic elements in the +II oxidation state is highlighted. Throughout, the symbiotic interplay of experimental and computational studies is emphasized; the extraordinary challenges of experimental transuranic chemistry afford computational chemistry a particularly valuable role at the frontier of the periodic table.

  • Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of AnIV(Aracnac)4 Complexes (An = Th, U, Np, Pu; Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-tBu2C6H3)
    Inorganic chemistry, 2012
    Co-Authors: David D. Schnaars, Nikolas Kaltsoyannis, Andrew J. Gaunt, Trevor W. Hayton, Matthew B. Jones, Ian Kirker, Iain May, Sean D. Reilly, Brian L. Scott

    Abstract:

    A Series of tetravalent An(IV) complexes with a bis-phenyl β-ketoiminate N,O donor ligand has been synthesized with the aim of identifying bonding trends and changes across the Actinide Series. The neutral molecules are homoleptic with the formula An(Aracnac)4 (An = Th (1), U (2), Np (3), Pu (4); Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-tBu2C6H3) and were synthesized through salt metathesis reactions with Actinide chloride precursors. NMR and electronic absorption spectroscopy confirm the purity of all four new compounds and demonstrate stability in both solution and the solid state. The Th, U, and Pu complexes were structurally elucidated by single-crystal X-ray diffraction and shown to be isostructural in space group C2/c. Analysis of the bond lengths reveals shortening of the An–O and An–N distances arising from the Actinide contraction upon moving from 1 to 2. The shortening is more pronounced upon moving from 2 to 4, and the steric constraints of the tetrakis complexes appear to prevent the enhanced U–O …

Brian L. Scott – One of the best experts on this subject based on the ideXlab platform.

  • Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of AnIV(Aracnac)4 Complexes (An = Th, U, Np, Pu; Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-tBu2C6H3)
    Inorganic chemistry, 2012
    Co-Authors: David D. Schnaars, Nikolas Kaltsoyannis, Andrew J. Gaunt, Trevor W. Hayton, Matthew B. Jones, Ian Kirker, Iain May, Sean D. Reilly, Brian L. Scott

    Abstract:

    A Series of tetravalent An(IV) complexes with a bis-phenyl β-ketoiminate N,O donor ligand has been synthesized with the aim of identifying bonding trends and changes across the Actinide Series. The neutral molecules are homoleptic with the formula An(Aracnac)4 (An = Th (1), U (2), Np (3), Pu (4); Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-tBu2C6H3) and were synthesized through salt metathesis reactions with Actinide chloride precursors. NMR and electronic absorption spectroscopy confirm the purity of all four new compounds and demonstrate stability in both solution and the solid state. The Th, U, and Pu complexes were structurally elucidated by single-crystal X-ray diffraction and shown to be isostructural in space group C2/c. Analysis of the bond lengths reveals shortening of the An–O and An–N distances arising from the Actinide contraction upon moving from 1 to 2. The shortening is more pronounced upon moving from 2 to 4, and the steric constraints of the tetrakis complexes appear to prevent the enhanced U–O …

  • Challenging the metallocene dominance in Actinide chemistry with a soft PNP pincer ligand: new uranium structures and reactivity patterns.
    Angewandte Chemie (International ed. in English), 2009
    Co-Authors: Thibault Cantat, Brian L. Scott, Christopher R. Graves, Jaqueline L. Kiplinger

    Abstract:

    A soft embrace for U: Replacement of C(5)Me(5) by the soft PNP pincer ligand is a successful strategy to promote new reactivities and support new structures for the Actinide Series (see picture, py-O = pyridine-N-oxide). The specific electronic and steric properties of the PNP ligand enable access to previously unreported structures not available for the C(5)Me(5) ligand set and support not only low-valent uranium but also the high-valent uranium(VI) ion.

  • A Simple Preparative Route to Bis(imido)uranium(VI) Complexes by the Direct Reductions of Diazenes and Azides.
    Angewandte Chemie (International ed. in English), 1998
    Co-Authors: Benjamin P. Warner, Brian L. Scott, Carol J. Burns

    Abstract:

    In clean, one-pot procedures, the uranium complex 1 reductively cleaves azides and azo compounds to generate bis(imido) derivatives [Eq. (a)]. This unusual reaction has not been observed previously in either the Actinide Series or with a metallocene complex.