Bent cis d0 MoO22+ vs. linear trans d0f0 UO22+: a significant role for nonvalence 6p orbitals in uranyl

Tatsumi, Kazuyuki; Hoffmann, Roald

doi:10.1021/ic50211a035

Cited by 178 publications

(127 citation statements)

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“…As shown by the NLMO results and the orbital contributions listed in Tables 3 and 4, the threefold symmetry of the X 3 U'CR molecules allows significant hybridization or orbital mixing between U 6d and 5f orbitals, which enhances the bonding strengths of the U'C triple bonds. Table 4 also reveals that the -bond of F 3 U'CH molecule involves nonnegligible U 6p hybridization with 5f/6d orbitals, similar to the ''pushing from below'' 6p-5f mixing in uranyl (64).…”

Section: Resultsmentioning

confidence: 82%

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

Lyon

Andrews

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

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Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X 3U'CH (X ‫؍‬ F, Cl, Br), F2ClU'CH, and F 3U'CF formed through reactions of laser-ablated uranium atoms and trihalomethanes or carbon tetrafluoride in excess argon. By using matrix infrared spectroscopy and relativistic quantum chemistry calculations, we have shown that these actinide complexes possess relatively strong U'C triple bonds between the U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-withdrawing ligands are critical in stabilizing the U(VI) oxidation state and sustaining the formation of uranium multiple bonds. These unique U'C-bearing molecules are examples of the long-sought actinide-alkylidynes. This discovery opens the door to the rational synthesis of triple-bonded actinide-carbon compounds.actinide multiple bond ͉ heavy element ͉ laser ablation ͉ matrix isolation ͉ relativistic quantum chemistry

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Section: Resultsmentioning

confidence: 82%

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

Lyon

Andrews

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

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“…The importance of the 6p pseudocore has also been illustrated in several theoretical studies, [69] and in an elegant study of [UO 2 Cl 4 ] 2À by polarized oxygen K-edge X-ray absorption and emission spectroscopy.…”

Section: In the Case Of [Uocl 5 ]mentioning

confidence: 93%

Evaluating f‐Element Bonding from Structure and Thermodynamics

Minasian

Krinsky

Arnold

2011

Chemistry A European J

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The practical goal to measure and understand the thermodynamic properties of molecules and materials containing f-elements is often achieved through indirect methods. Of the characterization tools available to inorganic chemists, few are more powerful than X-ray crystallography. Yet for lanthanides and actinides, interpretation of a bond length is a challenging undertaking that involves a complex interplay of steric and electronic forces. In this Concept article, we perform an analysis of selected examples in which structural criteria alone have been used to draw qualitative conclusions about chemical bonding. In other instances for which such an analysis is not valid, thermodynamic information is evaluated side by side with structural data to provide reasonable interpretations of a covalent/ionic mode of bonding. A geometric variation larger than 3σ is not necessarily correlated to a change in bonding, nor is an increase in bond energy related to a bond with more covalent character. However, careful consideration of thermodynamic information can lead to reasonable interpretations of electronic structure, and may provide a more reliable benchmark for the theoretical methods which can describe f-elements.

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“…This stems from the fact that contrary to the zigzag ordering, it does not benefit from forming stronger bonds via the most favourable cis interaction between the Ti-3d and the N-2p orbitals 37 . Indeed, as shown in Table S2 †, both models have longer Ti-N bonds compared to the zigzag arrangements.…”

Section: Bulk Ordering and Electronic Structurementioning

confidence: 98%

Surface structure and anion order of the oxynitride LaTiO₂N

Ninova

2017

J. Mater. Chem. A

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Oxynitrides are promising materials for water splitting under visible light. Members of this class of semiconductors that crystallise in the perovskite structure are often characterised by O/N disorder, while some studies observe 2D cischain ordering of the M-N-M bonds in the bulk. Despite the fact that the surface structure and composition is expected to have a significant influence on the surface chemistry and therefore the photocatalytic activity, little is known about the O/N arrangement at surfaces of these materials. In the present study, we investigate the surface structure of LaTiO 2 N, a particularly promising candidate for water splitting, using density functional theory (DFT) calculations. Based on slab calculations with different anion order we find that the N atoms prefer to form trans-chains at the (001) surface, as opposed to the bulk. This is governed by the electrostatic stability that is optimal for alternating charge-neutral (LaN)-(TiO 2 ) atomic layers. We show that polar surfaces that do not fulfil this requirement will electronically or structurally reconstruct. Our results predict that in contact with vacuum, the LaTiO 2 N (001) surface will preferentially be LaN-terminated.

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Bent cis d0 MoO22+ vs. linear trans d0f0 UO22+: a significant role for nonvalence 6p orbitals in uranyl

Cited by 178 publications

References 0 publications

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

Evaluating f‐Element Bonding from Structure and Thermodynamics

Surface structure and anion order of the oxynitride LaTiO₂N

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Bent cis d0 MoO22+ vs. linear trans d0f0 UO22+: a significant role for nonvalence 6p orbitals in uranyl

Cited by 178 publications

References 0 publications

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

Evaluating f‐Element Bonding from Structure and Thermodynamics

Surface structure and anion order of the oxynitride LaTiO2N

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Product

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Surface structure and anion order of the oxynitride LaTiO₂N