Liberation of three dihydrogens from two ethene molecules as mediated by the tantalum nitride anion cluster Ta3N2− at room temperature

Hu, Ji-Chuang; Xu, Linlin; Li, Haifang; Valdivielso, David Yubero; Fielicke, André; He, Sheng‐Gui; Ma, Jia-Bi

doi:10.1039/c6cp06896k

Cited by 8 publications

(6 citation statements)

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“…Quantum-chemical calculations were performed to study the structures of Ta 3 N 3 – and Ta 3 N 3 H – clusters and the mechanistic details of the reactions. As predicted by B3LYP-D3, which was adopted for other Ta x N y – systems, the energy difference of the two isomers for Ta 3 N 3 H – is within 0.11 eV, as shown in Figure a, and other calculated structures are given in Figure S3. Since the accuracy of the B3LYP functional is not better than ±0.1 eV, the single-point energies of isomers for Ta 3 N 3 H 0,1 – were recalculated by the high-level CCSD(T)-F12.…”

Section: Resultssupporting

confidence: 52%

Dinitrogen Fixation and Reduction by Ta₃N₃H_0,1^– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

et al. 2019

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Dinitrogen activation and reduction is one of the most challenging and important subjects in chemistry. Herein, we report the N 2 binding and reduction at the well-defined Ta 3 N 3 H − and Ta 3 N 3 − gas-phase clusters by using mass spectrometry (MS), anion photoelectron spectroscopy (PES), and quantum-chemical calculations. The PES and calculation results show clear evidence that N 2 can be adsorbed and completely activated by Ta 3 N 3 H − and Ta 3 N 3 − clusters, yielding to the products Ta 3 N 5 H − and Ta 3 N 5 − , but the reactivity of Ta 3 N 3 H − is five times higher than that of the dehydrogenated Ta 3 N 3 − clusters. The detailed mechanistic investigations further indicate that a dissociative mechanism dominates the N 2 activation reactions mediated by Ta 3 N 3 H − and Ta 3 N 3 − ; two and three Ta atoms are active sites and also electron donors for the N 2 reduction, respectively. Although the hydrogen atom in Ta 3 N 3 H − is not directly involved in the reaction, its very presence modifies the charge distribution and the geometry of Ta 3 N 3 H − , which is crucial to increase the reactivity. The mechanisms revealed in this gas-phase study stress the fundamental rules for N 2 activation and the important role of transition metals as active sites as well as the new significant role of metal hydride bonds in the process of N 2 reduction, which provides molecular-level insights into the rational design of tantalum nitride-based catalysts for N 2 fixation and activation or NH 3 synthesis.

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Section: Resultssupporting

confidence: 52%

Dinitrogen Fixation and Reduction by Ta₃N₃H_0,1^– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

et al. 2019

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“…24 The reaction of a tantalum nitride cluster anion was reported as well; Ta 3 N 2 À reacts with two ethene molecules to form Ta 3 N 2 C 4 H 2 À along with release of three hydrogen molecules. 25 The reaction of ammonia with the tantalum monomer cation and small neutral tantalum-oxide clusters has also been reported. 26,27 The tantalum monomer cation, Ta + , reacts with ammonia molecules to form TaNH(NH 3 ) n + (n = 0, 2, 3)…”

Section: Introductionmentioning

confidence: 97%

The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules

Arakawa

Ando

Fujimoto

et al. 2018

Phys. Chem. Chem. Phys.

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Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.

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“…Hu et al found that Becke's three-parameter hybrid density functional with the Lee-Yang-Parr correlation functional (B3LYP) provided accurate predictions of Ta-N, N-N, C-H, and N-H bond dissociation energies for Ta 3 N 2 À . 103 We found the B3LYP functional to be quite accurate in predicting metal-N and metal-O vibrations.…”

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confidence: 81%

Zooming in on the initial steps of catalytic NO reduction using metal clusters

Bakker

Mafuné

2022

Phys. Chem. Chem. Phys.

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Liberation of three dihydrogens from two ethene molecules as mediated by the tantalum nitride anion cluster Ta₃N₂⁻ at room temperature

Cited by 8 publications

References 58 publications

Dinitrogen Fixation and Reduction by Ta₃N₃H_0,1^– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

Dinitrogen Fixation and Reduction by Ta₃N₃H_0,1^– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules

Zooming in on the initial steps of catalytic NO reduction using metal clusters

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Liberation of three dihydrogens from two ethene molecules as mediated by the tantalum nitride anion cluster Ta3N2− at room temperature

Cited by 8 publications

References 58 publications

Dinitrogen Fixation and Reduction by Ta3N3H0,1– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

Dinitrogen Fixation and Reduction by Ta3N3H0,1– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules

Zooming in on the initial steps of catalytic NO reduction using metal clusters

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Product

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Liberation of three dihydrogens from two ethene molecules as mediated by the tantalum nitride anion cluster Ta₃N₂⁻ at room temperature

Dinitrogen Fixation and Reduction by Ta₃N₃H_0,1^– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity

Dinitrogen Fixation and Reduction by Ta₃N₃H_0,1^– Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity