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Taming the Antiferromagnetic Beast: Computational Design of Ultrashort Mn−Mn Bonds Stabilized by N‐Heterocyclic Carbenes
Author(s) -
Francisco Marcos A. S.,
Fantuzzi Felipe,
Cardozo Thiago M.,
Esteves Pierre M.,
Engels Bernd,
Oliveira Ricardo R.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101116
Subject(s) - singlet state , manganese , carbene , computational chemistry , chemistry , antiferromagnetism , adiabatic process , metal , chemical physics , materials science , photochemistry , atomic physics , physics , thermodynamics , condensed matter physics , catalysis , organic chemistry , excited state
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 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.