There is much interest in the reduction and reductive coupling of carbon monoxide (CO) and isocyanides (CNR) under mild transition metal catalyzed conditions, yet the cleavage of the C-O or C-N bond remains a challenging step. We recently reported a series of [TmR’Fe(CNR)3](OTf) complexes (Tm = tris(mercaptoimidazolyl)hydroborate) (R = tBu, Ad, R’ = Me, Ph, Mes) that, upon treatment with KC8, water and air, generate the corresponding (di-)tert-butylurea. This transformation involves reduction of the isocyanide ligand to the corresponding amine (H2NR) accomplishing the challenging C-N bond cleavage step. To better understand the nature of the reduced intermediate(s) an extended series of tripodal iron isocyanide complexes of the type [TmR’Fe(CNR)3](OTf) (R = tBu, Bn, Cy, Ad, R’ = Me, Ph, Bn, Mes) has been synthesized and their reductions have been investigated using a combination of spectroscopic techniques and electrochemical measurements. Understanding the electronic structures of these intermediates and their ability to enable the C-N bond cleavage may lead to improved systems for CO and CNR reduction and reductive coupling.

Influence of the isocyanide and Tm ligands on the reductive coupling of [TmR’Fe(CNR)3]OTf

255th National Meeting (2018)

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