22999-67-3Relevant academic research and scientific papers
Aryl-containing chelates and amine debenzylation to afford 1,3-di-2-pyridyl-2-azaallyl (smif): Structures of {κ-C,N,N py2-(2-pyridylmethyl)2N(CH2(4- tBu-phenyl-2-yl))}FeBr and (smif)CrN(TMS)2
Frazier, Brenda A.,Wolczanski, Peter T.,Lobkovsky, Emil B.
, p. 11576 - 11585 (2010/04/25)
Aryl-bromide ligand precursors have been prepared with the potential to afford tetradentate chelates (2-pyridylmethyl)3-xN(CH 2-2-Aryl)x (x = 1, 2) containing metal-aryl linkages that promise to impart stronger fields abou
Synthesis of [2Fe-2S] and [4Fe-4S] clusters having terminal amide ligands from an iron(II) amide complex
Ohki, Yasuhiro,Sunada, Yusuke,Tatsumi, Kazuyuki
, p. 172 - 173 (2007/10/03)
The reaction of iron(II) bis-amide Fe{N(SiMe3)2} 2 with elemental sulfur afforded a direct entry to new [Fe 2S2] and [Fe2S4] clusters with terminal amide groups, Fe4S4{N(SiMe3) 2}4 (1) and Fe2S2{N(SiMe 3)2}2(tmtu)2 (2), whose structures have been determined by X-ray crystallography. Tetrameric cubane cluster 1 exhibits one reversible and one quasireversible processes in the cyclic voltammetry, whereas dimeric rhombus complex 2 reveals one irreversible reduction process. Copyright
Iron-arylimide clusters [Fem(NAr)nCl4]2- (m, n = 2, 2; 3, 4; 4, 4) from a ferric amide precursor: Synthesis, characterization, and comparison to Fe-S chemistry
Duncan, Jeremiah S.,Nazif, Tamim M.,Verma, Atul K.,Lee, Sonny C.
, p. 1211 - 1224 (2008/10/08)
Tetrahedral FeCl[N(SiMe3)2]2(THF) (2), prepared from FeCl3 and 2 equiv of Na[N(SiMe3)2] in THF, is a useful ferric starting material for the synthesis of weak-field iron-imide (Fe-NR) clusters. Protonolysis of 2 with aniline yields azobenzene and [Fe2(μ-Cl)3(THF)6]2 [Fe3(μ-NPh)4Cl4] (3), a salt composed of two diferrous monocations and a trinuclear dianion with a formal 2 Fe(III)/1 Fe(IV) oxidation state. Treatment of 2 with LiCl, which gives the adduct [FeCl2{N(SiMe3)2}2]- (isolated as the [Li(TMEDA)2]+ salt), suppresses arylamine oxidation/iron reduction chemistry during protonolysis. Thus, under appropriate conditions, the reaction of 1:1 2/LiCl with arylamine provides a practical route to the following Fe-NR clusters: [Li2(THF)7][Fe3(μ-NPh) 4Cl4] (5a), which contains the same Fe-NR cluster found in 3; [Li(THF)4]2[Fe3(μ-N-p-Tol) 4Cl4] (5b); [Li(DME)3]2[Fe2(μ-NPh) 2Cl4] (6a); [Li2(THF)7][Fe2(μ-NMes) 2Cl4] (6c). [Li(DME)3]2[Fe4(μ 3-NPh)4Cl4] (7), a trace product in the synthesis of 5a and 6a, forms readily as the sole Fe-NR complex upon reduction of these lower nuclearity clusters. Products were characterized by X-ray crystallographic analysis, by electronic absorption, 1H NMR, and Moessbauer spectroscopies, and by cyclic voltammetry. The structures of the Fe-NR complexes derive from tetrahedral iron centers, edge-fused by imide bridges into linear arrays (5a,b; 6a,c) or the condensed heterocubane geometry (7), and are homologous to fundamental iron-sulfur (Fe-S) cluster motifs. The analogy to Fe-S chemistry also encompasses parallels between Fe-mediated redox transformations of nitrogen and sulfur ligands and reductive core conversions of linear dinuclear and trinuclear clusters to heterocubane species and is reinforced by other recent examples of iron- and cobalt-imide cluster chemistry. The correspondence of nitrogen and sulfur chemistry at iron is intriguing in the context of speculative Fe-mediated mechanisms for biological nitrogen fixation.
