A Comprehensive Analysis of the Metal–Nitrile Bonding in an Organo-Diiron System

Nitriles (N≡CR) are ubiquitous in coordination chemistry, yet literature studies on metal–nitrile bonding based on a multi-technique approach are rare. We selected an easily-available di-organoiron framework, containing both π-acceptor (CO, aminocarbyne) and donor (Cp = η(5)−C(5)H(5)) ligands, as a suitable system to provide a comprehensive description of the iron–nitrile bond. Thus, the new nitrile (2–12)CF(3)SO(3) and the related imine/amine complexes (8–9)CF(3)SO(3) were synthesized in 58–83% yields from the respective tris-carbonyl precursors (1a–d)CF(3)SO(3), using the TMNO strategy (TMNO = trimethylamine-N-oxide). The products were fully characterized by elemental analysis, IR (solution and solid state) and multinuclear NMR spectroscopy. In addition, the structures of (2)CF(3)SO(3), (3)CF(3)SO(3), (5)CF(3)SO(3) and (11)CF(3)SO(3) were ascertained by single crystal X-ray diffraction. Salient spectroscopic data of the nitrile complexes are coherent with the scale of electron-donor power of the R substituents; otherwise, this scale does not match the degree of Fe → N π-back-donation and the Fe–N bond energies, which were elucidated in (2–7)CF(3)SO(3) by DFT calculations.