Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)3− and OUFe(CO)3− Complexes

Chi, Chaoxian; Wang, Jiaqi; Qu, Hui; Li, Wan‐Lu; Meng, Luyan; Luo, Mingbiao; Li, Jun; Zhou, Mingfei

doi:10.1002/ange.201703525

Cited by 12 publications

(3 citation statements)

References 57 publications

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“…Interestingly, such a molecule was reported recently by Knecht et al and shown by state-of-the-art relativistic quantumchemical calculations to contain a quadruple bond (24). Two recent landmark experimental advances in this field are the generation of a U-Fe triple bond in the gas phase under laser vaporization by Zhou and coworkers (25) and the synthesis of a double-dative bond between Rh and U by Liddle and coworkers (26).…”

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confidence: 96%

Identification of a uranium–rhodium triple bond in a heterometallic cluster

Feng

Zhang

Wang

et al. 2019

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

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The chemistry of d-block metal–metal multiple bonds has been extensively investigated in the past 5 decades. However, the synthesis and characterization of species with f-block metal–metal multiple bonds are significantly more challenging and such species remain extremely rare. Here, we report the identification of a uranium–rhodium triple bond in a heterometallic cluster, which was synthesized under routine conditions. The uranium–rhodium triple-bond length of 2.31 Å in this cluster is only 3% longer than the sum of the covalent triple-bond radii of uranium and rhodium (2.24 Å). Computational studies reveal that the nature of this uranium–rhodium triple bond is 1 covalent bond with 2 rhodium-to-uranium dative bonds. This heterometallic cluster represents a species with f-block metal–metal triple bond structurally authenticated by X-ray diffraction. These studies not only demonstrate the authenticity of the uranium–metal triple bond, but also provide a possibility for the synthesis of other f-block metal–metal multiple bonds. We expect that this work may further our understanding of the bonding between uranium and transition metals, which may help to design new d-f heterometallic catalysts with uranium–metal bonds for small-molecule activation and to promote the utilization of abundant depleted uranium resources.

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confidence: 96%

Identification of a uranium–rhodium triple bond in a heterometallic cluster

Feng

Zhang

Wang

et al. 2019

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

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“…In 2001, the cationic species [OUFe(CO) 3 ] + was generated in the gas phase in a FTICR mass spectrometer, by reacting the uranium oxide cation UO + with Fe(CO) 5 [113]. Recently, Zhou and co-workers used a laser-vaporization supersonic ion source to produce the anions [UFe(CO) 5 ]-and [OUFe(CO) 3 ] − in the gas phase, characterized by infrared photo dissociation spectroscopy [114]. Quantum chemical studies were consistent with a uraniumiron triple bond, one covalent σ bond and two Fe-to-U dative π bonds, and a formal charge of 2-for iron.…”

Section: Uranium-transition Metal Complexesmentioning

confidence: 99%

Uranyl Analogue Complexes—Current Progress and Synthetic Challenges

Maria

Marçalo

2022

Inorganics

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Uranyl ions, {UO2}n+ (n = 1, 2), display trans, strongly covalent, and chemically robust U-O multiple bonds, where 6d, 5f, and 6p orbitals play important roles. The synthesis of isoelectronic analogues of uranyl has been of interest for quite some time, mainly with the purpose of unveiling covalence and 5f-orbital participation in bonding. Significant advances have occurred in the last two decades, initially marked by the synthesis of uranium(VI) bis(imido) complexes, the first analogues with a {RNUNR}2+ core, later followed by the synthesis of unique trans-{EUO}2+ (E = S, Se) complexes, and recently highlighted by the synthesis of the first complexes featuring a linear {NUN} moiety. This review covers the synthesis, structure, bonding, and reactivity of uranium complexes containing a linear {EUE}n+ core (n = 0, 1, 2), isoelectronic to uranyl ions, {OUO}n+ (n = 1, 2), incorporating σ- and π-donating ligands that can engage in uranium–ligand multiple bonding, where oxygen may be replaced by heavier chalcogenido, imido, nitride, and carbene ligands, or by a transition metal. It focuses on synthetic methods of well-defined molecular uranium species in the condensed phase but also references gas-phase and low-temperature-matrix experiments, as well as computational studies that may lead to valuable insights.

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“…28 Heterodinuclear iron oxide carbonyls, represented by OUFe(CO) 3 − , exhibit an identical chemical bonding profile to UFe(CO) 3 − . 25 So far, heterodinuclear metal oxide carbonyls simultaneously containing both main group and transition metals remain unexplored. Given the significant role of heterobinuclear oxide carbonyls in CO oxidation via the Langmuir−Hinshelwood-like mechanism, further research in this field is warranted.…”

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confidence: 99%

Observation of the Transition from Triple Bonds to Single Bonds between Ru–Ge Bonding in RuGeO(CO)_n^– (n = 3–5)

Zhang,

Ling,

et al. 2024

J. Phys. Chem. Lett.

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This work reports the observation and characterization of heterobinuclear transition-metal main-group metal oxide carbonyl complex anions, RuGeO(CO) n − (n = 3−5), by combining mass-selected photoelectron velocity map imaging spectroscopy and quantum chemistry calculations. The experimentally determined vertical electron detachment energy of RuGeO(CO) 3 − surpasses those of RuGeO(CO) 4 − and RuGeO(CO) 5 − , which is attributed to distinctive bonding features. RuGeO(CO) 3 − manifests one covalent σ and two Ru-to-Ge dative π bonds, contrasting with the sole covalent σ bond present in RuGeO(CO) 4 − and RuGeO(CO) 5 − . Unpaired spin density distribution analysis reveals a 17-electron configuration at the Ru center in RuGeO(CO) 3 − and an 18-electron configuration in RuGeO(CO) 4 − and RuGeO(CO) 5 − . This work closes a gap in the quantitative physicochemical characterization of heteronuclear oxide carbonyl complexes, enhancing our insights into catalytic processes of CO/GeO on the metal surface at the molecular level.

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Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)₃⁻ and OUFe(CO)₃⁻ Complexes

Cited by 12 publications

References 57 publications

Identification of a uranium–rhodium triple bond in a heterometallic cluster

Identification of a uranium–rhodium triple bond in a heterometallic cluster

Uranyl Analogue Complexes—Current Progress and Synthetic Challenges

Observation of the Transition from Triple Bonds to Single Bonds between Ru–Ge Bonding in RuGeO(CO)_n^– (n = 3–5)

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Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)3− and OUFe(CO)3− Complexes

Cited by 12 publications

References 57 publications

Identification of a uranium–rhodium triple bond in a heterometallic cluster

Identification of a uranium–rhodium triple bond in a heterometallic cluster

Uranyl Analogue Complexes—Current Progress and Synthetic Challenges

Observation of the Transition from Triple Bonds to Single Bonds between Ru–Ge Bonding in RuGeO(CO)n– (n = 3–5)

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Preparation and Characterization of Uranium–Iron Triple‐Bonded UFe(CO)₃⁻ and OUFe(CO)₃⁻ Complexes

Observation of the Transition from Triple Bonds to Single Bonds between Ru–Ge Bonding in RuGeO(CO)_n^– (n = 3–5)