Mononuclear, Dinuclear, and Trinuclear Iron Complexes Featuring a New Monoanionic SNS Thiolate Ligand
详细信息 查看全文
- 作者：Uttam K. Das ; Stephanie L. Daifuku ; Serge I. Gorelsky ; Ilia Korobkov ; Michael L. Neidig ; Jennifer J. Le Roy ; Muralee Murugesu ; R. Tom Baker
- 刊名：Inorganic Chemistry
- 出版年：2016
- 出版时间：January 19, 2016
- 年：2016
- 卷：55
- 期：2
- 页码：987-997
- 全文大小：578K
- ISSN：1520-510X
文摘
The new tridentate ligand, SMeNHS = 2-(2-methylthiophenyl)benzothiazolidine, prepared in a single step from commercial precursors in excellent yield, undergoes ring-opening on treatment with Fe(OTf)2 in the presence of base affording a trinuclear iron complex, [Fe3(μ2-SMeNS–)4](OTf)2 (1) which is fully characterized by structural and spectroscopic methods. X-ray structural data reveal that 1 contains four SMeNS– ligands meridionally bound to two pseudooctahedral iron centers each bridged by two thiolates to a distorted tetrahedral central iron. The combined spectroscopic (UV–vis, M?ssbauer, NMR), magnetic (solution and solid state), and computational (DFT) studies indicate that 1 includes a central, high-spin Fe(II) (S = 2) with two low-spin (S = 0) peripheral Fe(II) centers. Complex 1 reacts with excess PMePh2, CNxylyl (2,6-dimethylphenyl isocyanide), and P(OMe)3 in CH3CN to form diamagnetic, thiolate-bridged, dinuclear Fe(II) complexes {[Fe(μ-SMeNS–)L2]2}(OTf)2 (2–4). These complexes are characterized by elemental analysis; 1H NMR, IR, UV–vis, and M?ssbauer spectroscopy; and single crystal X-ray diffraction. Interestingly, addition of excess P(OMe)3 to complex 1 in CH2Cl2 produces primarily the diamagnetic, mononuclear Fe(II) complex, {Fe(SMeNS–)[P(OMe)3]3}(OTf) (5).