Reaction of Laser-Ablated Uranium and Thorium Atoms with H<sub>2</sub>Se: A Rare Example of Selenium Multiple Bonding

Vent‐Schmidt, Thomas; Andrews, Lester; Thanthiriwatte, K. Sahan; Dixon, David A.; Riedel, Sebastian

doi:10.1021/acs.inorgchem.5b01383

Cited by 15 publications

(9 citation statements)

References 57 publications

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“…As listed in Tables S1 and S2, the calculated B3LYP NBO analysis for OMS, OM(η 2 -SO), and OM(η 2 -SO)(η 2 -O 2 S) shows that for Ce–O/Ce–S π bonds over 98% p character is on the O or S to the Ce or Th. The cases of dative electron donation were also reported in our earlier papers. − …”

Section: Resultssupporting

confidence: 78%

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

Huang

Wang

et al. 2018

J. Phys. Chem. A

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Infrared absorptions of the matrix isolated OMS, OM(η-SO), and OM(η-SO)(η-OS) (M = Ce, Th) molecules were observed following reactions of laser-ablated Ce and Th metal atoms with SO during condensation in excess argon and neon. Band assignments for the main vibrational modes were confirmed by appropriate SO and SO isotopic shifts. B3LYP, BPW91 density functional, and CASSCF/CASPT2 calculations were performed to characterize these new reaction products and to explore the admixture of f orbitals into the bonding giving stronger M≡O triple bonds. It is very interesting that both OM(η-SO) and OM(η-SO)(η-OS) molecules show chiral structure.

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Section: Resultssupporting

confidence: 78%

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

Huang

Wang

et al. 2018

J. Phys. Chem. A

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“…Subsequently, the nodal properties of the 5 f -orbitals led Streitwieser and colleagues to predict the existence of actinocenes. − More recently, 5 f - and 6 d -orbital participation in bonding has been used to explain the existence and stability of many actinide functional groups, i.e. actinide–ligand multiple bonds, ,− actinide–arene delta interactions, ,− and molecular actinide–metal bonds. − The invocation of orbital mixing in these seminal publications motivated our efforts to directly evaluate orbital mixing in an americium–ligand bond.…”

Section: Introductionmentioning

confidence: 99%

Covalency in Americium(III) Hexachloride

et al. 2017

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Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance of orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by Seaborg and co-workers ( Diamond, R. M.; Street, K., Jr.; Seaborg, G. T. J. Am. Chem. Soc. 1954 , 76 , 1461 ) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in-arguably-one of the most difficult systems to study, the Am-Cl interaction within AmCl. We observed both 5f- and 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl indicated that the amount of Cl 3p-mixing with Eu 5d-orbitals was similar to that observed with the Am 6d-orbitals. Meanwhile, the results confirmed Seaborg's 1954 hypothesis that Am 5f-orbital covalency was more substantial than 4f-orbital mixing for Eu.

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“…Thorium–ligand multiple bond chemistry is an attractive area for studying chemical bonding because of the intrinsic features of metal–ligand multiple bonds, but it is far less developed than uranium1234, being restricted to a few carbene21252627282930, imido313233 and chalcogenido222324343536 complexes. Very recently the first thorium–phosphinidene and μ-phosphido complexes under ambient conditions37 added to the preparation of a thorium–phosphido complex in frozen argon matrix isolation conditions38.…”

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confidence: 99%

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

et al. 2017

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Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

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Reaction of Laser-Ablated Uranium and Thorium Atoms with H₂Se: A Rare Example of Selenium Multiple Bonding

Cited by 15 publications

References 57 publications

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

Covalency in Americium(III) Hexachloride

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

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Reaction of Laser-Ablated Uranium and Thorium Atoms with H2Se: A Rare Example of Selenium Multiple Bonding

Cited by 15 publications

References 57 publications

OMS, OM(η2-SO), and OM(η2-SO)(η2-O2S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

OMS, OM(η2-SO), and OM(η2-SO)(η2-O2S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

Covalency in Americium(III) Hexachloride

Triamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs

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Product

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Reaction of Laser-Ablated Uranium and Thorium Atoms with H₂Se: A Rare Example of Selenium Multiple Bonding

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations

OMS, OM(η²-SO), and OM(η²-SO)(η²-O₂S) Molecules (M = Ce, Th) with Chiral Structure: Matrix Infrared Spectra and Theoretical Calculations