Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Inorg Chem. 2011 Feb 21;50(4):1551-62. doi: 10.1021/ic1021627. Epub 2011 Jan 20.
The reaction of Fe(N{SiMe(3)}(2))(2) (1) with 1 equiv of arylthiol (ArSH) results in material of notional composition Fe(SAr)(N{SiMe(3)}(2)) (2), from which crystalline Fe(2)(μ-SAr)(2)(N{SiMe(3)}(2))(2)(THF)(2) (Ar = Mes) can be isolated from tetrahydrofuran (THF) solvent. Treatment of 2 with 0.5 equiv of 1,2-diarylhydrazine (Ar'NH-NHAr', Ar' = Ph, p-Tol) yields ferric-imide-thiolate cubanes Fe(4)(μ(3)-NAr')(4)(SAr)(4) (3). The site-differentiated, 1-electron reduced iron-imide cubane derivative [Fe(THF)(6)]Fe(4)(μ(3)-N-p-Tol)(4)(SDMP)(3)(N{SiMe(3)}(2)) ([Fe(THF)(6)]4; DMP = 2,6-dimethylphenyl) can be isolated by adjusting the reaction stoichiometry of 1/ArSH/Ar'NHNHAr' to 9:6:5. The isolated compounds were characterized by a combination of structural (X-ray diffraction), spectroscopic (NMR, UV-vis, Mössbauer, EPR), and magnetochemical methods. Reactions with a range of hydrazines reveal complex chemical behavior that includes not only N-N bond reduction for 1,2-di- and trisubstituted arylhydrazines, but also catalytic disproportionation for 1,2-diarylhydrazines, N-C bond cleavage for 1,2-diisopropylhydrazine, and no reaction for hindered and tetrasubstituted hydrazines.
Fe(N{SiMe(3)}(2))(2)（1）与 1 当量的芳基硫醇（ArSH）反应得到名义组成为 Fe(SAr)(N{SiMe(3)}(2))（2）的物质，从四氢呋喃（THF）溶剂中可以分离出结晶的 Fe(2)(μ-SAr)(2)(N{SiMe(3)}(2))(2)(THF)(2)（Ar = Mes）。将 2 与 0.5 当量的 1,2-二芳基腙（Ar'NH-NHAr'，Ar' = Ph，p-Tol）反应生成铁酰亚胺-硫代酸盐立方烷 Fe(4)(μ(3)-NAr')(4)(SAr)(4)（3）。通过调节 1/ArSH/Ar'NHNHAr'的反应化学计量比为 9:6:5，可以分离出具有位点区分的、单电子还原的铁酰亚胺立方烷衍生物[Fe(THF)(6)]Fe(4)(μ(3)-N-p-Tol)(4)(SDMP)(3)(N{SiMe(3)}(2)) ([Fe(THF)(6)]4；DMP = 2,6-二甲基苯基)。所分离的化合物通过结构（X 射线衍射）、光谱（NMR、UV-vis、Mössbauer、EPR）和磁化学方法进行了表征。与一系列肼的反应揭示了复杂的化学行为，不仅包括 1,2-二取代和三取代芳基肼的 N-N 键还原，还包括 1,2-二芳基肼的催化歧化、1,2-二异丙基肼的 N-C 键断裂以及受阻和四取代肼的无反应。
