Steric Congestion at, and Proximity to, a Ferrous Center Leads to Hydration of α‑Nitrile Substituents Forming Coordinated Carboxamides

• Published in: Inorganic chemistry 2014-08, Vol.53 (15), p.7824-7836
• Main Authors: Thallaj, Nasser K, Orain, Pierre-Yves, Thibon, Aurore, Sandroni, Martina, Welter, Richard, Mandon, Dominique
• Format: Article
• Language: English
• Subjects: Amides - chemistry; Chemical Sciences; Ferrous Compounds - chemistry; Ligands; Nitriles - chemistry; X-Ray Diffraction
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic500096h

The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.