title: Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I).
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 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(I){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 [Mn(I){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.
authors.affiliation: CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, 31077 Toulouse (France) and Université de Toulouse, UPS, INPT, 31077, Toulouse, France.
authors.forename: C Gunnar
authors.initials: CG
authors.lastname: Werncke
authors.affiliation: Max-Planck-Institute for Chemical Energy Conversion, Stiftstrasse 34-36, Mühlheim an der Ruhr, 45470, Germany.
authors.forename: Elizaveta
authors.initials: E
authors.lastname: Suturina
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, California, 94720, USA.
authors.forename: Philip C
authors.initials: PC
authors.lastname: Bunting
authors.affiliation: CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, 31077 Toulouse (France) and Université de Toulouse, UPS, INPT, 31077, Toulouse, France.
authors.forename: Laure
authors.initials: L
authors.lastname: Vendier
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, California, 94720, USA.
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Long
authors.affiliation: Max-Planck-Institute for Chemical Energy Conversion, Stiftstrasse 34-36, Mühlheim an der Ruhr, 45470, Germany. mihail.atanasov@cec.mpg.de.|Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria. mihail.atanasov@cec.mpg.de.
authors.forename: Mihail
authors.initials: M
authors.lastname: Atanasov
authors.affiliation: Max-Planck-Institute for Chemical Energy Conversion, Stiftstrasse 34-36, Mühlheim an der Ruhr, 45470, Germany. frank.neese@cec.mpg.de.
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
authors.affiliation: CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, 31077 Toulouse (France) and Université de Toulouse, UPS, INPT, 31077, Toulouse, France.
authors.forename: Sylviane
authors.initials: S
authors.lastname: Sabo-Etienne
authors.affiliation: CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, 31077 Toulouse (France) and Université de Toulouse, UPS, INPT, 31077, Toulouse, France. sebastien.bontemps@lcc-toulouse.fr.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Bontemps
keywords: N ligands; ab initio calculations; coordination modes; magnetic properties; transition metals