The role of bridging ligands in dinitrogen reduction and functionalization by uranium multimetallic complexes

Falcone, Marta; Barluzzi, Luciano; Andrez, Julie; Fadaei‐Tirani, Farzaneh; Živković, Ivica; Fabrizio, Alberto; Corminbœuf, Clémence; Severin, Kay; Mazzanti, Marinella

doi:10.1038/s41557-018-0167-8

Cited by 116 publications

(129 citation statements)

References 45 publications

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“…The N 2 reduction and industrial Haber-Bosch processes for ammonia synthesis are thought to involve multimetallic catalytic sites. Uranium species exhibits promising properties in small-molecule activation (40)(41)(42)(43)(44)(45)(46). The dative U ← Rh bonds in the d-f heterometallic clusters 2 and 3 are advantageous for synergistic substrate activation through the polarized U-Rh bond.…”

Section: Significancementioning

confidence: 99%

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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Section: Significancementioning

confidence: 99%

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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“…More recently, computational studies showed a marked covalent character of the K3U III NU III with a U-N bond order of 1.4. 66 Please do not adjust margins Please do not adjust margins…”

Section: Reaction With Metal Azides: Synthesis Of Uranium Nitridesmentioning

confidence: 99%

“…N2 activation and functionalization by oxide bridged diuranium(III) complexesThe highly reducing nature of the[K2{[U(OSi(O t Bu)3)3]2(μ-O)}], K2U-O-U,22 was evidenced by its reactivity with the inert N2 molecule that affords the dinitrogen complex[K2{[U(OSi(O t Bu)3)3]2(µ-O)(µ-h 2 :h 2 -N2)}], 51 66. The N2 binding and functionalization reactivity of 22 is summarized in Scheme 23.The crystallographically determined N-N bond distance together with SQUID magnetometry measurements confirmed the nature of the U centres in 51 to be U(V), in agreement with the presence of a bound N2 4ligand.…”

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confidence: 99%

Small molecule activation by multimetallic uranium complexes supported by siloxide ligands

2019

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“…2,[8][9][10][11][12][13][14][15][16][17][18][19][20][21] The study of these complexes has allowed actinide chemists to reveal fundamentally important insights into 5f covalency, as well as uncover novel modes of reactivity. 12,[15][16][17][18][22][23][24] In contrast, no isolable molecular thorium nitride complexes are known. 25 A handful of thorium nitrides have been identied in matrix isolation studies, such as ThN, NThN, and NThO, but these are only stable at cryogenic temperatures.…”

Section: Introductionmentioning

confidence: 99%