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

C. Gunnar Werncke, Elizaveta Suturina, Philip C. Bunting, Laure Vendier, Jeffrey R. Long, Mihail Atanasov, Frank Neese, Sylviane Sabo-Etienne, Sébastien Bontemps

Research output: Contribution to journalArticlepeer-review

34 Citations (Scopus)

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]2 2- 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.

Original languageEnglish
Pages (from-to)1668-1674
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number5
Early online date18 Dec 2015
DOIs
Publication statusPublished - 26 Jan 2016

Keywords

  • ab initio calculations
  • coordination modes
  • magnetic properties
  • N ligands
  • transition metals

ASJC Scopus subject areas

  • Chemistry(all)

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