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Homoleptic Two‐Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I)

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Suturina,  Elizaveta A.
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Atanasov,  Mihail
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Werncke, G., Suturina, E. A., Bunting, P. C., Vendier, L., Long, J. R., Atanasov, M., et al. (2016). Homoleptic Two‐Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I). Chemistry – A European Journal, 22(5), 1668-1674. doi:10.1002/chem.201503980.


Cite as: http://hdl.handle.net/21.11116/0000-0007-84FF-5
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.