Homoleptic two-coordinate silylamido complexes of chromium(I), manganese(I), and cobalt(I)

C. Gunnar Werncke (1, 2) , Elizaveta Suturina (3) , Philip C. Bunting (4) , Laure Vendier (1) , Jeffrey R. Long (5) , Mihail Atanasov (3, 6) , Frank Neese (3) , Sylviane Sabo-Etienne (1) , Sébastien Bontemps (1)

1 LCC - Laboratoire de chimie de coordination
2 UT3 - Université Toulouse III - Paul Sabatier
3 Max Planck Institute for Chemical Energy Conversion
4 UC Berkeley - University of California [Berkeley]
5 Department of Chemistry [Berkeley]
6 Institute of General and Inorganic Chemistry

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 Fe-I complexes even in the presence of a Lewis base. We now report analogous Cr-I and Co-I complexes with exclusively this amido ligand and the isolation of a [Mn-IN(SiMe3)(2)(2)](2)(2-) dimer that features a Mn Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two-coordinate complex [Mn-IN(Dipp)(SiMe3)(2)](-) was isolated (Dipp= 2,6-iPr(2)-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.

Domaines: Chimie de coordination

C. Gunnar Werncke, Elizaveta Suturina, Philip C. Bunting, Laure Vendier, Jeffrey R. Long, et al.. Homoleptic two-coordinate silylamido complexes of chromium(I), manganese(I), and cobalt(I). Chemistry - A European Journal, 2016, 22 (5), pp.1668-1674. ⟨10.1002/chem.201503980⟩. ⟨hal-01933178⟩