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Identification of a uranium-rhodium triple bond in a heterometallic cluster.

ABSTRACT: 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.

SUBMITTER: Feng G

PROVIDER: S-EPMC6731654 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Identification of a uranium-rhodium triple bond in a heterometallic cluster.

Feng Genfeng G Zhang Mingxing M Wang Penglong P Wang Shuao S Maron Laurent L Zhu Congqing C

Proceedings of the National Academy of Sciences of the United States of America 20190819 36

The chemistry of <i>d</i>-block metal-metal multiple bonds has been extensively investigated in the past 5 decades. However, the synthesis and characterization of species with <i>f</i>-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 clust ...[more]

PMID: 31427529

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Project description:Understanding the fundamental properties governing metal-metal interactions is crucial to understanding the electronic structure and thereby applications of multimetallic systems in catalysis, material science, and magnetism. One such property that is relatively underexplored within multimetallic systems is metal-metal bond polarity, parameterized by the electronegativities (χ) of the metal atoms involved in the bond. In heterobimetallic systems, metal-metal bond polarity is a function of the donor-acceptor (Δχ) interactions of the two bonded metal atoms, with electropositive early transition metals acting as electron acceptors and electronegative late transition metals acting as electron donors. We show in this work, through the preparation and systematic study of a series of Mo2M(dpa)4(OTf)2 (M = Cr, Mn, Fe, Co, and Ni; dpa = 2,2'-dipyridylamide; OTf = trifluoromethanesulfonate) heterometallic extended metal atom chain (HEMAC) complexes that this expected trend in χ can be reversed. Physical characterization via single-crystal X-ray diffraction, magnetometry, and spectroscopic methods as well as electronic structure calculations supports the presence of a σ symmetry 3c/3e- bond that is delocalized across the entire metal-atom chain and forms the basis of the heterometallic Mo2-M interaction. The delocalized 3c/3e- interaction is discussed within the context of the analogous 3c/3e- π bonding in the vinoxy radical, CH2CHO. The vinoxy comparison establishes three predictions for the σ symmetry 3c/3e- bond in HEMACS: (1) an umpolung effect that causes the Mo-M interactions to become more covalent as Δχ increases, (2) distortion of the σ bonding and non-bonding orbitals to emphasize Mo-M bonding and de-emphasize Mo-Mo bonding, and (3) an increase in Mo spin population with increasing Mo-M covalency. In agreement with these predictions, we find that the Mo2···M covalency increases with increasing Δχ of the Mo and M atoms (ΔχMo-M increases as M = Cr < Mn < Fe < Co < Ni), an umpolung of the trend predicted in the absence of σ delocalization. We attribute the observed trend in covalency to the decreased energic differential (ΔE) between the heterometal dz2 orbital and the σ bonding molecular orbital of the Mo2 quadruple bond, which serves as an energetically stable, "ligand"-like electron-pair donor to the heterometal ion acceptor. As M is changed from Cr to Ni, the σ bonding and nonbonding orbitals do indeed distort as anticipated, and the spin population of the outer Mo group is increased by at least a factor of 2. These findings provide a predictive framework for multimetallic compounds and advance the current understanding of the electronic structures of molecular heteromultimetallic systems, which can be extrapolated to applications in the context of mixed-metal surface catalysis and multimetallic proteins.

Dataset Information

Identification of a uranium-rhodium triple bond in a heterometallic cluster.

Publications

Identification of a uranium-rhodium triple bond in a heterometallic cluster.

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