Cleavage of the N<sub>2</sub> Triple Bond by the Ti Dimer: A Route to Molecular Materials for Dinitrogen Activation?

Himmel, Hans‐Jörg; Hübner, Olaf; Klopper, Wim; Manceron, L.

doi:10.1002/anie.200503709

Cited by 70 publications

(59 citation statements)

References 21 publications

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“…[103] In the course of this reaction, the NÀN triple bond is completely cleaved with the formation of a four-membered, planar [Ti 2 N 2 ] ring compound. The experiments have been repeated with different dinitrogen isotopomers.…”

Section: Groupmentioning

confidence: 99%

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Himmel¹,

Reiher²

2006

Angew Chem Int Ed

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119

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There is ongoing interest in metal complexes which bind dinitrogen and facilitate either its reduction or oxidation under mild conditions. In nature, the enzyme nitrogenase catalyzes this process, and dinitrogen fixation occurs under mild and ambient conditions at a metal-sulfur cluster in the center of the MoFe protein, but the mechanism of this process remains largely unknown. In the last few years, new important discoveries have been made in this field. In this review are discussed recent findings on the interaction of N(2) with metal atoms and metal-atom dimers from all groups of the periodic table as provided by gas-phase as well as matrix-isolation experiments. Intrinsic dinitrogen activation at such bare metal atoms is then related to corresponding processes at complexes, clusters, and surfaces.

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Section: Groupmentioning

confidence: 99%

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Himmel¹,

Reiher²

2006

Angew Chem Int Ed

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119

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“…The reactivity of metal atoms and dimers toward N 2 was reviewed in 2006 . Sc 2 , Y 2 , La 2 and Ti 2 react spontaneously with N 2 to form Sc 2 N 2 and Ti 2 N 2 to break the strong triple bond (see Scheme ) . One of the bands of the Ti 2 N 2 product in the IR spectrum is shown in Figure .…”

Section: Metal Atom Clustersmentioning

confidence: 99%

“…One of the bands of the Ti 2 N 2 product in the IR spectrum is shown in Figure . The bands due to each isotopologue are split into three components due to the polycrystalline matrix host (“matrix splitting”) . Ti 2 N 2 reacts further with an excess N 2 to give presumably [Ti 2 N 2 (μ‐N 2 )(N 2 ) 8 ] (see Scheme ) .…”

Section: Metal Atom Clustersmentioning

confidence: 99%

“…[248] Sc 2 ,Y 2 ,L a 2 and Ti 2 react spontaneously with N 2 to form Sc 2 N 2 and Ti 2 N 2 to break the strong triple bond (see Scheme14). [228][229][230][231] One of the bands of the Ti 2 N 2 product in the IR spectrum is shown in Figure 13. The bandsd ue to each isotopologue are split into three components due to the polycrystalline matrix host ("matrixs plitting").…”

Section: Reactions Of MC Lusters In Matricesmentioning

confidence: 99%

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Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Hübner

Himmel

2018

Chemistry A European J

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Metal cluster models are of high relevance for establishing new mechanistic concepts for heterogeneous catalysis. The high reactivity and particular selectivity of metal clusters is caused by the wealth of low-lying electronically excited states that are often thermally populated. Thereby the metal clusters are flexible with regard to their electronic structure and can adjust their states to be appropriate for the reaction with a particular substrate. The matrix isolation technique is ideally suited for studying excited state reactivity. The low matrix temperatures (generally 4-40 K) of the noble gas matrix host guarantee that all clusters are in their electronic ground-state (with only a very few exceptions). Electronically excited states can then be selectively populated and their reactivity probed. Unfortunately, a systematic research in this direction has not been made up to date. The purpose of this review is to provide the grounds for a directed approach to understand cluster reactivity through matrix-isolation studies combined with quantum chemical calculations.

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“…Several dinitrogen titanium sandwich complexes have been synthesized [53][54][55], but none of them were successful for the hydrogenation of N 2 . Recently, a matrix isolation study showed that the ''naked'' Ti 2 dimer cleaves the NaN triple bond of N 2 and forms (TiN) 2 species without a significant energy barrier [56].…”

Section: 4mentioning

confidence: 99%

Principles of Dinitrogen Hydrogenation: Computational Insights

Musaev

Bobadova‐Parvanova²,

Morokuma

2008

Computational Modeling for Homogeneous and Enzymatic Catalysis

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Cleavage of the N₂ Triple Bond by the Ti Dimer: A Route to Molecular Materials for Dinitrogen Activation?

Abstract: The Ti dimer is fairly weakly bound, but highly reactive, and completely cleaves the strong N2 triple bond in just one step without activation energy (see scheme; Ti red, N blue). In contrast, a Ti atom in its ground electronic state does not react with N2.

Cited by 70 publications

References 21 publications

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Principles of Dinitrogen Hydrogenation: Computational Insights

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Cleavage of the N2 Triple Bond by the Ti Dimer: A Route to Molecular Materials for Dinitrogen Activation?

Abstract: The Ti dimer is fairly weakly bound, but highly reactive, and completely cleaves the strong N2 triple bond in just one step without activation energy (see scheme; Ti red, N blue). In contrast, a Ti atom in its ground electronic state does not react with N2.

Cited by 70 publications

References 21 publications

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Principles of Dinitrogen Hydrogenation: Computational Insights

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Product

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Cleavage of the N₂ Triple Bond by the Ti Dimer: A Route to Molecular Materials for Dinitrogen Activation?