Linear, Trinuclear Cobalt Complexes with o ‐Phenylene‐bis‐Silylamido Ligands

Transamination of [Co{N(SiMe 3 ) 2 } 2 ] 2 with C 6 H 4 (NHSi i Pr 3 ) 2 gave the centrosymmetric trinuclear [{Co ter N(SiMe 3 ) 2 (μ‐η‐[ o ‐C 6 H 4 ( κ NSi i Pr 3 ) 2 ])} 2 Co int ] ( 1 ) (Co ter , Co int =terminal, internal Co, respectively), with 3‐coordinate Co ter , and Co int “sandwiched” between the o ‐phenylenes of the two ligands; experimental and computational data support Co II centres and ditopic o ‐amido‐imino‐cyclohexen‐allyl ligands; magnetic studies reveal intermetallic ferromagnetic interactions and single‐molecule magnet (SMM) character. One‐electron reduction of 1 yielded the salt [K(18‐crown‐6)(THF) 2 ][{Co ter N(SiMe 3 ) 2 (μ‐η‐[ o ‐C 6 H 4 ( κ NSi i Pr 3 ) 2 ])} 2 Co int ] ( 4 ) with the anion isostructural to 1 . The centrosymmetric Fe complex [{Fe ter N(SiMe 3 ) 2 (μ‐η‐[ o ‐C 6 H 4 ( κ NSi i Pr 3 ) 2 ])} 2 Fe int ] ( 5 ), analogous to 1 , was also obtained.