Abstract

AbstractHerein we report the first mesoionic carbene (MIC)‐Mn(I) complex Mn‐bim‐MICimz derived from imidazolylidene motif. Structurally the octahedral Mn(I) complex Mn‐bim‐MICimz was assembled with an anionic benzimidazolato‐anchored imidazolylidene MIC‐based bidentate ligand (bim‐MICimz) and four CO ligands, as supported by detailed characterization using NMR and FTIR spectroscopy, mass spectrometry, and single crystal X‐ray diffraction study. We reckoned that the bim‐MICimz ligand would provide a robust and stable bonding with the Mn(I) centre, and also enhance electron density at the Mn(I) centre through its stronger σ‐donating/weaker π‐accepting property. These structural and electronic attributes triggered to exploit Mn‐bim‐MICimz in catalytic hydrogenation of N‐heteroarenes, where efficient hydride (Mn−H) delivery is a key step.

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