title: The reactions of pyridinyl thioesters with triiron dodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations.
abstract: Reaction of Fe(3)(CO)(12) with pyridinyl thioester ligand PyCH(2)SCOCH(3) (L(1), Py = pyridin-2-yl) produced complex, [Fe(2)(κ-COCH(3))(μ-SCH(2)Py)(CO)(5)] (1) (PyCH(2)S = pyridin-2-ylmethanethiolate). When complex 1 reacted with PPh(3), a monosubstituted complex, [Fe(2)(κ-COCH(3))(μ-SCH(2)Py)(CO)(4)PPh(3)] (2), was derived. Reaction of the same precursor with analogous thioester ligand PyCH(2)SCOPy (L(2)) generated three novel diiron complexes, [Fe(2)(κ-Py)(μ-SCH(2)Py)(CO)(5)] (3), [Fe(2)(κ-Py)'(μ-SCH(2)Py)(CO)(5)] (4), and [Fe(2)(κ-Py)(μ-SCH(2)Py)(CO)(6)] (5). Complexes 3 and 4 are structural isomers. Complex 5 could be converted into complex 4 but the conversion from complex 5 to the isomer 3 was not observed. All the five complexes were fully characterised using FTIR, NMR, and other techniques. Their structures were determined using X-ray single crystal diffraction analysis. The oxidative formation of complexes 1, 3, 4, and 5 involved C-S and/or C-C bonds cleavages. To probe possible mechanisms for these cleavages, DFT calculations were performed. From the calculations, viable reaction pathways leading to the formation of all the isolated products were delineated. The results of the theoretic calculations also allowed rationalisation of the experimental observations.
authors: Department of Chemistry, Nanchang University, Nanchang 330031, China.
authors: Li
authors: L
authors: Long
authors: Zhiyin
authors: Z
authors: Xiao
authors: Giuseppe
authors: G
authors: Zampella
authors: Zhenhong
authors: Z
authors: Wei
authors: Luca
authors: L
authors: De Gioia
authors: Xiaoming
authors: X
authors: Liu
mesh_terms: D004952:Esters / Q000737:chemistry*; D054354:Iron Carbonyl Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D017550:Spectroscopy, Fourier Transform Infrared; D013457:Sulfur Compounds / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D004952:Esters; D013457:Sulfur Compounds; D054354:Iron Carbonyl Compounds