Diiron Aminocarbyne Complexes with NCE - Ligands (E = O, S, Se)

• Published in: Molecules (Basel, Switzerland) Switzerland), 2023-04, Vol.28 (7), p.3251
• Main Authors: Bresciani, Giulio, Zacchini, Stefano, Pampaloni, Guido, Bortoluzzi, Marco, Marchetti, Fabio
• Format: Article
• Language: English
• Subjects: Acetone; Acetonitrile; aminocarbyne ligand; Carbon; Chemical properties; Coordination; Cyanides; Dichloromethane; diiron complexes; Ligands; Magnetic resonance spectroscopy; Molecular structure; Nitrogen; NMR; NMR spectroscopy; Nuclear magnetic resonance; organometallic chemistry; Organometallic compounds; Room temperature; Selenium; selenocyanate; Single crystals; Substitution reactions; Thermal properties; X-ray diffraction
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules28073251

Diiron μ-aminocarbyne complexes [Fe Cp (NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF SO (R = Xyl, ; R = Me, ; R = Cy, ; R = CH Ph, ), freshly prepared from tricarbonyl precursors , reacted with NaOCN (in acetone) and NBu SCN (in dichloromethane) to give [Fe Cp (k -NCO)(CO)(μ-CO){μ-CN(Me)(R)}] (R = Xyl, ; Me, ; Cy, ) and [Fe Cp (k -NCS)(CO)(μ-CO){μ-CN(Me)(CH Ph)}], in 67-81% yields via substitution of the acetonitrile ligand. The reaction of with KSeCN in THF at reflux temperature led to the cyanide complexes [Fe Cp (CN)(CO)(μ-CO){μ-CNMe(R)}], - (45-67%). When the reaction of with KSeCN was performed in acetone at room temperature, subsequent careful chromatography allowed the separation of moderate amounts of [Fe Cp (k -SeCN)(CO)(μ-CO){μ-CN(Me)(Xyl)}], , and [Fe Cp (k -NCSe)(CO)(μ-CO){μ-CN(Me)(Xyl)}], . All products were fully characterized by elemental analysis, IR, and multinuclear NMR spectroscopy; moreover, the molecular structure of was ascertained by single crystal X-ray diffraction. DFT calculations were carried out to shed light on the coordination mode and stability of the {NC -} fragment.