Homoleptic Two‐Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I) |
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| Authors: | Dr C Gunnar Werncke Dr Elizaveta Suturina Philip C Bunting Dr Laure Vendier Prof Jeffrey R Long Prof?Dr Mihail Atanasov Prof?Dr Frank Neese Dr Sylviane Sabo‐Etienne Dr Sébastien Bontemps |
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| Affiliation: | 1. CNRS, LCC (Laboratoire de Chimie de Coordination), Toulouse, France;2. Max-Planck-Institute for Chemical Energy Conversion, Mühlheim an der Ruhr, Germany;3. Department of Chemistry, University of California, Berkeley, Berkeley, California, USA;4. Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria;5. http://www.lcc‐toulouse.fr/lcc/spip.php?article433 |
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| 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)(SiMe3)}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. |
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| Keywords: | ab initio calculations magnetic properties N ligands transition metals coordination modes |
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