Taming the Antiferromagnetic Beast: Computational Design of Ultrashort Mn-Mn Bonds Stabilized by N-Heterocyclic Carbenes

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 eta(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.

Automated summary

This study discusses the design principles and computational investigation of new organometallic platforms containing stable manganese-manganese bonds. The analysis focuses on the metal-carbene interaction and auxiliary coordination to generate short metal-metal bonds, closed-shell singlet multiplicities, and positive singlet-triplet energy gaps. The research identifies two classes of viable synthetic targets with thoroughly investigated electrostructural properties.