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ab initio calculations; magnetic properties; N ligands; transition metals; coordination modes
Abstract:
Anionic two‐coordinate complexes of first‐row transition‐metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe3)2− ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two‐coordinate FeI complexes even in the presence of a Lewis base. We now report analogous CrI and CoI complexes with exclusively this amido ligand and the isolation of a [MnI{N(SiMe3)2}2]22− dimer that features a Mn−Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two‐coordinate complex [MnI{N(Dipp)(SiMe)}2]− was isolated (Dipp=2,6‐iPr2‐C6H3). Characterisation of these compounds by using X‐ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand‐field analysis based on CASSCF/NEVPT2 ab initio calculations.
