1. Pogo-Stick Iron and Cobalt Complexes: Synthesis, Structures, and Magnetic Properties
- Author
-
Marius Peters, Dirk Baabe, Marc D. Walter, Miyuki Maekawa, Dirk Bockfeld, Matthias Tamm, and Marc-Kevin Zaretzke
- Subjects
010405 organic chemistry ,Coordination number ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Magnetic susceptibility ,0104 chemical sciences ,law.invention ,Inorganic Chemistry ,Metal ,Crystallography ,chemistry ,law ,visual_art ,Atom ,Mössbauer spectroscopy ,Salt metathesis reaction ,visual_art.visual_art_medium ,Physical and Theoretical Chemistry ,Electron paramagnetic resonance ,Cobalt - Abstract
The synthesis, structures, and magnetic properties of monomeric half-sandwich iron and cobalt imidazolin-2-iminato complexes have been comprehensively investigated. Salt metathesis reactions of [Cp'M(μ-I)]2 (1-M, M = Fe, Co; Cp' = η5-1,2,4-tri-tert-butylcyclopentadienyl) with [ImDippNLi]2 (ImDippN = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) furnishes the terminal half-sandwich compounds [Cp'M(NImDipp)] (2-M, M = Fe, Co), which can be regarded as models for elusive half-sandwich iron and cobalt imido complexes. X-ray diffraction analysis confirmed the structure motif of a one-legged piano stool. Complex 2-Co can also be prepared by an acid-base reaction between [Cp'Co{N(SiMe3)2}] (3-Co) and ImDippNH. The electronic and magnetic properties of 2-M and 3-Co were probed by 57Fe Mossbauer spectroscopy (M = Fe), X-band EPR spectroscopy (M = Co), and solid-state magnetic susceptibility measurements. In particular, the central metal atom adopts a high-spin (S = 2) state in 2-Fe, while the cobalt complex 2-Co represents a rare example of a Co(II) species with a coordination number different from six displaying a low-spin to high-spin spin-crossover (SCO) behavior. The experimental observations are complemented by DFT calculations.
- Published
- 2019
- Full Text
- View/download PDF