Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions.

Autor: Inchausti A; MALTA-Consolider Team and Departamento de Química Física, Universidad Complutense de Madrid, Plz. Ciencias 2, Madrid, E-28040, Spain., Mollfulleda R; Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi, Parc UdG, Catalonia, Girona, E-17003, Spain., Swart M; Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi, Parc UdG, Catalonia, Girona, E-17003, Spain.; ICREA Pg. Lluís Companys 23, Barcelona, 08010, Spain., Perles J; Laboratorio de Difracción de Rayos X de Monocristal, Servicio Interdepartamental de Investigación, Universidad Autónoma de Madrid, Madrid, E-28049, Spain., Herrero S; MatMoPol Research Group, Departamento de Química Inorgánica, Universidad Complutense de Madrid, Plz. Ciencias 2, Madrid, E-28040, Spain., Baonza VG; MALTA-Consolider Team and Departamento de Química Física, Universidad Complutense de Madrid, Plz. Ciencias 2, Madrid, E-28040, Spain., Taravillo M; MALTA-Consolider Team and Departamento de Química Física, Universidad Complutense de Madrid, Plz. Ciencias 2, Madrid, E-28040, Spain., Lobato Á; MALTA-Consolider Team and Departamento de Química Física, Universidad Complutense de Madrid, Plz. Ciencias 2, Madrid, E-28040, Spain.
Jazyk: angličtina
Zdroj: Advanced science (Weinheim, Baden-Wurttemberg, Germany) [Adv Sci (Weinh)] 2024 Jul; Vol. 11 (25), pp. e2401293. Date of Electronic Publication: 2024 Apr 03.
DOI: 10.1002/advs.202401293
Abstrakt: Previous studies on bimetallic paddlewheel compounds have established a direct correlation between metal-metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal-metal bond distances. Here, the new discovery based on diarylformamidinate Ru₂⁵⁺ paddlewheel compounds [Ru 2 Cl(DArF) 4 ] that show an opposite behavior is reported: higher torsions lead to shorter metal-metal distances. This discovery challenges the assumption that internal rotation solely impacts the δ bond. By combining experimental and theoretical techniques, it is demostrated that this trend is associated with previously overlooked π metal-ligand interactions. These π metal-ligand interactions are a direct consequence of the paddlewheel structure and the conjugated nature of the bidentate ligands. This findings offer far-reaching insights into the influence of equatorial ligands and their π-conjugation characteristics on the electronic properties of paddlewheel complexes. That this effect is not exclusive of diruthenium compounds but also occurs in other bimetallic cores such as ditungsten or dirhodium is demonstrated, and with other ligands showing allyl type conjugation. These results provide a novel approach for fine-tuning the properties of these compounds with significant implications for materials design.
(© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)
Databáze: MEDLINE
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