Taming the Antiferromagnetic Beast: Computational Design of Ultrashort Mn-Mn Bonds Stabilized by N-Heterocyclic Carbenes
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- The development of complexes featuring low-valent, multiply bonded metal centers is an exciting field with several potential applications. In this work, we describe the design principles and extensive computational investigation of new organometallic platforms featuring the elusive manganese-manganese bond stabilized by experimentally realized N-heterocyclic carbenes (NHCs). By using DFT computations benchmarked against multireference calculations, as well as MO- and VB-based bonding analyses, we could disentangle the various electronic andThe development of complexes featuring low-valent, multiply bonded metal centers is an exciting field with several potential applications. In this work, we describe the design principles and extensive computational investigation of new organometallic platforms featuring the elusive manganese-manganese bond stabilized by experimentally realized N-heterocyclic carbenes (NHCs). By using DFT computations benchmarked against multireference calculations, as well as MO- and VB-based bonding analyses, we could disentangle the various electronic and structural effects contributing to the thermodynamic and kinetic stability, as well as the experimental feasibility, of the systems. In particular, we explored the nature of the metal-carbene interaction and the role of the ancillary η\(^{6}\) coordination to the generation of Mn\(_{2}\) systems featuring ultrashort metal-metal bonds, closed-shell singlet multiplicities, and positive adiabatic singlet-triplet gaps. Our analysis identifies two distinct classes of viable synthetic targets, whose electrostructural properties are thoroughly investigated.…
Autor(en): | Marcos A. S. Franzsico, Felipe FantuzziORCiD, Thiago M. Cardozo, Pierre M. Esteves, Bernd Engels, Ricardo R. Oliveira |
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URN: | urn:nbn:de:bvb:20-opus-256874 |
Dokumentart: | Artikel / Aufsatz in einer Zeitschrift |
Institute der Universität: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Fakultät für Chemie und Pharmazie / Institut für Physikalische und Theoretische Chemie | |
Sprache der Veröffentlichung: | Englisch |
Titel des übergeordneten Werkes / der Zeitschrift (Englisch): | Chemistry—A European Journal |
Erscheinungsjahr: | 2021 |
Band / Jahrgang: | 27 |
Heft / Ausgabe: | 47 |
Seitenangabe: | 12126–12136 |
Originalveröffentlichung / Quelle: | Chemistry—A European Journal 2021, 27(47):12126–12136. DOI: 10.1002/chem.202101116 |
DOI: | https://doi.org/10.1002/chem.202101116 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Freie Schlagwort(e): | ab initio calculations; carbene ligands; density functional calculations; manganese; metal-metal interactions |
Datum der Freischaltung: | 08.03.2022 |
Lizenz (Deutsch): | CC BY-NC: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell 4.0 International |