Hydrogen Bonding to a Dinitrogen Complex at Room Temperature: Impacts on N<sub>2</sub> Activation

Shanahan, James P.; Szymczak, Nathaniel K.

doi:10.1021/jacs.9b02288

Cited by 43 publications

(38 citation statements)

References 59 publications

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“…S4). Therefore, pushing up the energies of π-backdonating orbitals may be a constructive strategy in the rational design of catalysts to ease the efficient cleavage of the N≡N bond (12,(58)(59)(60)(61)(62)(63)(64)(65).…”

Section: Significancementioning

confidence: 99%

Complete cleavage of the N≡N triple bond by Ta₂N⁺via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Geng

Weiske

et al. 2019

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

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An unprecedented, spontaneous, and complete cleavage of the triple bond of N2 in the thermal reaction of 15N2 with Ta214N+ was observed experimentally by Fourier transform ion cyclotron resonance mass spectrometry; mechanistic aspects of the degenerate ligand exchange were addressed by high-level quantum chemical calculations. The “hidden” dis- and reassembly of N2, mediated by Ta2N+, constitutes a full catalytic cycle. A frontier orbital analysis reveals that the scission of the N2 triple bond is essentially governed by the donation of d-electrons from the 2 metal centers into antibonding π*-orbitals of N2 and by the concurrent migration of electrons from bonding π- and σ-orbitals of N2 into empty d-orbitals of the metals. This work may contribute to a rational design of catalysts in order to reduce the still enormous energy demand required for an artificial dinitrogen activation.

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Section: Significancementioning

confidence: 99%

Complete cleavage of the N≡N triple bond by Ta₂N⁺via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Geng

Weiske

et al. 2019

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

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“…7a Structural, theoretical, and stability data are thus desirable for who wishes to exploit the reactivity of late TMs for the cooperative activation of N 2 . Moreover, the isolobal relationship existing between Au + and H + 15 makes the putative adducts relevant models to assess the effect of acidic residues on ligating N 2 within the active site of the nitrogenases and would come to complement the studies carried out by the Szymczak group, 11e , 16 whereas the paucity of reports of stable, genuine gold–N 2 complexes in the literature 17 provides further incentive to such investigations. Finally, the above-mentioned B(C 6 F 5 ) 3 -dinitrogen complexes can be well viewed as mixed metal/main group frustrated Lewis pairs (FLPs) 18 activating the N 2 molecule.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold Heterobimetallic Complexes

et al. 2021

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We have prepared and characterized a series of unprecedented group 6–group 11, N 2 -bridged, heterobimetallic [ML 4 (η 1 -N 2 )(μ-η 1 :η 1 -N 2 )Au(NHC)] + complexes (M = Mo, W, L 2 = diphosphine) by treatment of trans -[ML 4 (N 2 ) 2 ] with a cationic gold(I) complex [Au(NHC)] + . The adducts are very labile in solution and in the solid, especially in the case of molybdenum, and decomposition pathways are likely initiated by electron transfers from the zerovalent group 6 atom to gold. Spectroscopic and structural parameters point to the fact that the gold adducts are very similar to Lewis pairs formed out of strong main-group Lewis acids (LA) and low-valent, end-on dinitrogen complexes, with a bent M–N–N–Au motif. To verify how far the analogy goes, we computed the electronic structures of [W(depe) 2 (η 1 -N 2 )(μ-η 1 :η 1 -N 2 )AuNHC] + ( 10 W + ) and [W(depe) 2 (η 1 -N 2 )(μ-η 1 :η 1 -N 2 )B(C 6 F 5 ) 3 ] ( 11 W ). A careful analysis of the frontier orbitals of both compounds shows that a filled orbital resulting from the combination of the π* orbital of the bridging N 2 with a d orbital of the group 6 metal overlaps in 10 W + with an empty sd hybrid orbital at gold, whereas in 11 W with an sp 3 hybrid orbital at boron. The bent N–N–LA arrangement maximizes these interactions, providing a similar level of N 2 “push–pull” activation in the two compounds. In the gold case, the HOMO–2 orbital is further delocalized to the empty carbenic p orbital, and an NBO analysis suggests an important electrostatic component in the μ-N 2 –[Au(NHC)] + bond.

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“…During the last decade, substantial progress has been made in the study on the preparation and reactivity of rhenium‐dinitrogen complexes [18–21] . The typical examples are as follows.…”

Section: Methodsmentioning

confidence: 99%

Ammonia Formation Catalyzed by a Dinitrogen‐Bridged Dirhenium Complex Bearing PNP‐Pincer Ligands under Mild Reaction Conditions**

et al. 2021

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A series of rhenium complexes bearing a pyridine‐based PNP‐type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen‐bridged dirhenium complex bearing the PNP‐type pincer ligands catalytically converts dinitrogen into ammonia during the reaction with KC8 as a reductant and [HPCy3]BArF4 (Cy=cyclohexyl, ArF=3,5‐(CF3)2C6H3) as a proton source at −78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium‐dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC8 as a reductant and Me3SiCl as a silylating reagent under ambient reaction conditions to afford 11.7 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions using rhenium‐dinitrogen complexes as catalysts.

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Hydrogen Bonding to a Dinitrogen Complex at Room Temperature: Impacts on N₂ Activation

Cited by 43 publications

References 59 publications

Complete cleavage of the N≡N triple bond by Ta₂N⁺via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Complete cleavage of the N≡N triple bond by Ta₂N⁺via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold Heterobimetallic Complexes

Ammonia Formation Catalyzed by a Dinitrogen‐Bridged Dirhenium Complex Bearing PNP‐Pincer Ligands under Mild Reaction Conditions**

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Hydrogen Bonding to a Dinitrogen Complex at Room Temperature: Impacts on N2 Activation

Cited by 43 publications

References 59 publications

Complete cleavage of the N≡N triple bond by Ta2N+via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Complete cleavage of the N≡N triple bond by Ta2N+via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold Heterobimetallic Complexes

Ammonia Formation Catalyzed by a Dinitrogen‐Bridged Dirhenium Complex Bearing PNP‐Pincer Ligands under Mild Reaction Conditions**

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Product

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Hydrogen Bonding to a Dinitrogen Complex at Room Temperature: Impacts on N₂ Activation

Complete cleavage of the N≡N triple bond by Ta₂N⁺via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle

Complete cleavage of the N≡N triple bond by Ta₂N⁺via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle