Examining the relationship between coordination mode and reactivity of dinitrogen

Burford, Richard J.; Fryzuk, Michael D.

doi:10.1038/s41570-017-0026

Cited by 257 publications

(183 citation statements)

References 134 publications

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“…Worse still, the N 2 was repulsed to bind with the Rh atom and the RhÀ N bond attained 3.82 Å, suggested the weak physical adsorption was between the N 2 and RhN 4 . Energetically, we can find that the MoN 4 , WN 4 and RuN 4 model exhibited strong N 2 chemical adsorption with the adsorption energy values À 1.94 eV, À 1.43 eV and À 1.01 eV, respectively.…”

Section: N 2 Adsorption On Tmnmentioning

confidence: 89%

“…Ammonia synthesis is one of the most important issues for the production of nitrogen fertilizers and alternative hydrogen‐rich fuels, offering ways to improve food and energy production and environment sustainability . In the last century, the Haber‐Bosch method is the main industrial process of ammonia production . However, this method not only requires high temperature (300‐500 °C) and high pressure (100‐300 atm), but also generates ca.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] In the last century, the Haber-Bosch method is the main industrial process of ammonia production. [2,[4][5][6] However, this method not only requires high temperature (300-500°C) and high pressure (100-300 atm), but also generates ca. 1.9 metric tons of greenhouse gases.…”

Section: Introductionmentioning

confidence: 99%

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Transition Metal‐dinitrogen Complex Embedded Graphene for Nitrogen Reduction Reaction

et al. 2019

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Conversion of nitrogen to ammonia (NH3) is one of the most important issue in the modern chemical industry. Transition metals (TM) have the special unoccupied and occupied d orbitals to accept the electrons from and backdonate to N2, which is crucial in effective nitrogen reduction reaction (NRR). Herein, we propose TMN4 (TM=Fe, Co, Mo, W, Ru, Rh) embedded graphene as the catalysts for NRR by using the density functional theory calculations. Our results revealed that MoN4 embedded graphene exhibited outstanding catalytic activity for ammonia synthesis at ambient conditions along with small reaction energy barrier of 0.67 eV, as well as against hydrogen evolution reaction. These findings provide a potential paradigm for NRR.

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Section: N 2 Adsorption On Tmnmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

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Transition Metal‐dinitrogen Complex Embedded Graphene for Nitrogen Reduction Reaction

et al. 2019

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“…[19] Indeed, this type of reaction is dominated by dinuclear side-on-bound N 2 complexes.T he dititanium dinitrogen complex 2 is likely coaxed into forming NÀCb onds through the polarization of the Ti 2 N 2 core with coordinated potassium cations.F urther studies of this and related systems are in progress. These reactions represent rare examples of end-oncoordinated bridging N 2 ligands that form NÀCb onds to external electrophiles.The paucity of direct N 2 functionalization in the end-on bridging mode is presumably due to the absence of N 2 -based nonbonding electrons.…”

Section: Angewandte Chemiementioning

confidence: 99%

Nitrogen–Carbon Bond Formation by Reactions of a Titanium–Potassium Dinitrogen Complex with Carbon Dioxide, tert‐Butyl Isocyanate, and Phenylallene

2017

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Nitrogen-carbon bond-forming reactions at coordinated dinitrogen in a bifunctional titanium-potassium system are reported. A titanium atrane complex with a tris(aryloxide)methyl ligand (1) was treated with two equivalents of potassium naphthalenide under N atmosphere to generate a bifunctional complex (2) in which N binds end-on to two titanium centers and side-on to three potassium cations. Dinitrogen complex 2 reacted with carbon dioxide, tert-butyl isocyanate, and phenylallene, forming nitrogen-carbon bonds and affording diverse N-functionalized products. The reaction of 2 with CO followed by addition of Me SiCl resulted in the formation of the starting complex 1 with concomitant release of silylated carboxyl hydrazines while the reaction with two equivalents of tert-butyl isocyanate proceeded by insertion into the Ti-N bonds. Treatment of 2 with phenylallene afforded vinyl-substituted hydrazido complexes.

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“…Nevertheless, attachment of dinitrogen complexes to metal surfaces could provide significant advantages; for example, it may lower the activation energy required for the conversion of N 2 to ammonia in a sequence of protonation and reduction steps. Moreover, it may enable alternative pathways, such as the reaction of N 2 with H 2 under ambient conditions …”

Section: Introductionmentioning

confidence: 99%

Influence of a Metal Substrate on Small‐Molecule Activation Mediated by a Surface‐Adsorbed Complex

Schlimm

Stucke

Flöser

et al. 2018

Chemistry A European J

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Activating small molecules with transition metal complexes adsorbed on metal surfaces is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to study the influence of an Au(111) substrate on the activation of the small-molecule ligand carbon monoxide, a molybdenum tricarbonyl complex containing a PN P pincer ligand was synthesized and investigated in the bulk, in solution, and adsorbed on an Au(111) surface. By means of a platform approach, a perpendicular orientation of the molybdenum complex was achieved and confirmed by IRRAS and NEXAFS. By using vibrational spectroscopy (IR, Raman, IRRAS) coupled to DFT calculations, the influence of the metal substrate on the activation of the CO ligands bound to the molybdenum complex was determined. The electron-withdrawing behavior of gold causes an overall shift of the CO stretching vibrations to higher frequencies, which is partly compensated by dynamic charge transfer from the substrate to the molybdenum center, which increases its (dynamic) polarizability.

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Examining the relationship between coordination mode and reactivity of dinitrogen

Cited by 257 publications

References 134 publications

Transition Metal‐dinitrogen Complex Embedded Graphene for Nitrogen Reduction Reaction

Transition Metal‐dinitrogen Complex Embedded Graphene for Nitrogen Reduction Reaction

Nitrogen–Carbon Bond Formation by Reactions of a Titanium–Potassium Dinitrogen Complex with Carbon Dioxide, tert‐Butyl Isocyanate, and Phenylallene

Influence of a Metal Substrate on Small‐Molecule Activation Mediated by a Surface‐Adsorbed Complex

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