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Pogo-Stick Iron and Cobalt Complexes: Synthesis, Structures, and Magnetic Properties

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journal contribution
posted on 02.12.2019, 16:38 by Marius Peters, Dirk Baabe, Miyuki Maekawa, Dirk Bockfeld, Marc-Kevin Zaretzke, Matthias Tamm, Marc D. Walter
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 Mössbauer 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.