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Cooperative Dinitrogen Activation: Identifying the Push‐Pull Effects of Transition Metals and Lewis Acids in Molecular Orbital Diagrams

Martins, Frederico F. ; Krewald, Vera (2024)
Cooperative Dinitrogen Activation: Identifying the Push‐Pull Effects of Transition Metals and Lewis Acids in Molecular Orbital Diagrams.
In: European Journal of Inorganic Chemistry, 2023, 26 (35)
doi: 10.26083/tuprints-00027229
Artikel, Zweitveröffentlichung, Verlagsversion

Es ist eine neuere Version dieses Eintrags verfügbar.

URL / URN: https://tuprints.ulb.tu-darmstadt.de/27229

Kurzbeschreibung (Abstract)

The sustainable fixation of atmospheric N₂ and its conversion into industrially relevant molecules is one of the major current challenges in chemistry. Besides nitrogen activation with transition metal complexes, a "push‐pull" approach that fine‐tunes electron density along the N−N bond has shown success recently. The "pushing" is performed by an electron rich entity such as a transition metal complex, and the "pulling" is achieved with an electron acceptor such as a Lewis acid. In this contribution, we explore the electronic structure implications of this approach using the complex trans‐[ReᴵCl(N₂)(PMe₂Ph)₄] as a starting point. We show that borane Lewis acids exert a pull‐effect of increasing strength with increased Lewis acidity via a π‐pathway. Furthermore, the ligand trans to dinitrogen can weaken the dinitrogen bond via a σ‐pathway. Binding a strong Lewis acid is found to have electronic structure effects potentially relevant for electrochemistry: dinitrogen‐dominated molecular orbitals are shifted into advantageous energetic positions for redox activation of the dinitrogen bond. We show how these electronic structure design principles are rooted in cooperative effects of a transition metal complex and a Lewis acid, and that they can be exploited to tailor a complex towards the desired thermal, electrochemical or photochemical reactivity.

Typ des Eintrags:

Artikel

Erschienen:

2024

Autor(en):

Martins, Frederico F. ; Krewald, Vera

Art des Eintrags:

Zweitveröffentlichung

Titel:

Cooperative Dinitrogen Activation: Identifying the Push‐Pull Effects of Transition Metals and Lewis Acids in Molecular Orbital Diagrams

Sprache:

Englisch

Publikationsjahr:

27 Mai 2024

Ort:

Darmstadt

Publikationsdatum der Erstveröffentlichung:

12 Dezember 2023

Ort der Erstveröffentlichung:

Weinheim

Verlag:

Wiley-VCH

Titel der Zeitschrift, Zeitung oder Schriftenreihe:

European Journal of Inorganic Chemistry

Jahrgang/Volume einer Zeitschrift:

(Heft-)Nummer:

Kollation:

9 Seiten

DOI:

10.26083/tuprints-00027229

URL / URN:

https://tuprints.ulb.tu-darmstadt.de/27229

Zugehörige Links:

Verlags-DOI

Herkunft:

Zweitveröffentlichung DeepGreen

Kurzbeschreibung (Abstract):

Alternatives oder übersetztes Abstract:

Alternatives Abstract	Sprache
The cooperative "push-pull" effects of Reᴵ, Mo⁰, W⁰ complexes and borane Lewis acids on the dinitrogen bond are evaluated in molecular orbital diagrams: we extract electronic design principles in terms of orthogonal σ and π "push-pull" paths that may guide the design of complexes towards the desired thermal, electrochemical or photochemical reactivity of N₂.	Englisch

Freie Schlagworte:

Nitrogen Activation, Lewis Acids, Transition Metal Complexes, Push-Pull Effect, Electronic Structure

ID-Nummer:

Artikel-ID: e202300268

Status:

Verlagsversion

URN:

urn:nbn:de:tuda-tuprints-272295

Zusätzliche Informationen:

This article also appears in: Inorganic Reaction Mechanisms

Sachgruppe der Dewey Dezimalklassifikatin (DDC):

500 Naturwissenschaften und Mathematik > 540 Chemie