Thorium Mono- and Bis(imido) Complexes Made by Reprotonation of cyclo-Metalated Amides
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TLDR
X-ray and computational structural analyses show a "transition-metal-like" cis-bis(imido) geometry and polarized Th═N bonds with twice the Wiberg bond order of the formally single Th-N bond in the same molecule.Abstract:
Molecules containing actinide–nitrogen multiple bonds are of current interest as simple models for new actinide nitride nuclear fuels, and for their potential for the catalytic activation of inert hydrocarbon C–H bonds. Complexes with up to three uranium–nitrogen double bonds are now being widely studied, yet those with one thorium–nitrogen double bond are rare, and those with two are unknown. A new, simple mono(imido) thorium complex and the first bis(imido) thorium complex, K[Th(═NAr)N″3] and K2[Th(═NAr)2N″2], are readily made from insertion reactions (Ar = aryl, N″ = N(SiMe3)2) into the Th–C bond of the cyclometalated thorium amides [ThN″2(N(SiMe3)(SiMe2CH2))] and K[ThN″(N(SiMe3)(SiMe2CH2))2]. X-ray and computational structural analyses show a “transition-metal-like” cis-bis(imido) geometry and polarized Th═N bonds with twice the Wiberg bond order of the formally single Th–N bond in the same molecule.read more
Citations
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Use of 77Se and 125Te NMR Spectroscopy to Probe Covalency of the Actinide-Chalcogen Bonding in [Th(En){N(SiMe3)2}3]− (E = Se, Te; n = 1, 2) and Their Oxo-Uranium(VI) Congeners
TL;DR: X-ray diffraction studies together with NMR spectroscopic data and density functional theory (DFT) calculations provide convincing evidence for the actinide-chalcogen multiple bonding in the title complexes.
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Influence of the 5f Orbitals on the Bonding and Reactivity in Organoactinides: Experimental and Computational Studies on a Uranium Metallacyclopropene
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Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions.
TL;DR: 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 5 f- versus 6d -orbital composition and also significant involvement of the 7s-orbitals.
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Covalency in Americium(III) Hexachloride
Justin N. Cross,Jing Su,Enrique R. Batista,Samantha K. Cary,William J. Evans,Stosh A. Kozimor,Veronika Mocko,Brian L. Scott,Benjamin W. Stein,Cory J. Windorff,Cory J. Windorff,Ping Yang +11 more
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Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2015
TL;DR: A review of the progress in organo- f- element chemistry during the year 2015 can be found in this paper, where a number of interesting contributions have been published in the field of organolanthanide and organoactinide catalysis, with an emphasis on Ln-catalyzed olefin and diene polymerization.
References
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Journal ArticleDOI
Electronic Structure and Bonding in Actinyl Ions and their Analogs
TL;DR: This Feature Article seeks to present the current state of knowledge of the electronic structure and bonding in actinyl ions and related species, such as the isoelectronic imido compounds as well as in linear triatomic actinide molecules of the type X-An-Y.
Journal ArticleDOI
Methane and benzene activation via transient (tert-Bu3SiNH)2Zr:NSi-tert-Bu3
Journal ArticleDOI
Does covalency increase or decrease across the actinide series? Implications for minor actinide partitioning.
TL;DR: It is suggested that care must be taken when using quantum chemistry to assess metal-ligand covalency in this part of the periodic table and also topological analysis of the electron density via the quantum theory of atoms-in-molecules.
Journal ArticleDOI
Recent developments in actinide–ligand multiple bonding
TL;DR: Of particular note are the recent syntheses of the first isolable complex containing the nitride-substituted uranyl ion, [NUO](+), and the first report of an isolable terminal uranium nitride.
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Metal–ligand multiple bonding in uranium: structure and reactivity
TL;DR: Particular attention is focused on the recent developments in this area, such as the synthesis of the bis(imido) analogues of the uranyl ion, and the isolation of the first mu-nitrido complexes of this element.