State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, PR China, 200032.
Inorg Chem. 2013 Jan 7;52(1):59-65. doi: 10.1021/ic301894e. Epub 2012 Dec 18.
Using monodentate N-heterocyclic carbenes as the ancillary ligands, seven monomeric bis(anilido)iron(II) complexes [(IPr(2)Me(2))(2)Fe(NHAr)(2)] (IPr(2)Me(2) = 2,5-diisopropyl-3,4-dimethylimidazol-1-ylidene; Ar = Ph, C(6)H(4)-2-Pr(i), Mes, C(6)H(3)-2,6-Cl(2), Dipp) and [(IPr)Fe(NHAr)(2)] (IPr = 2,5-di(2,6-diisopropylphenyl)imidazol-1-ylidene; Ar = C(6)H(3)-2,6-Cl(2), Dipp) have been prepared by the one-pot reactions of Fe(Mes)(2) with the corresponding N-heterocyclic carbenes, and anilines. These high-spin diamido complexes have been fully characterized by (1)H NMR, solution magnetic susceptibility, UV-vis, IR, X-ray diffraction, cyclic voltammetry, as well as elemental analysis. The strong affinity of the N-heterocyclic carbene ligands toward ferrous centers, and the steric protection exerted by the NHC ligands are the key factors to stabilize these bis(anilido)iron complexes in a monomeric manner. Reactivity studies revealed the four-coordinate complex [(IPr(2)Me(2))(2)Fe(NHMes)(2)] can react with 1 equiv of 1-iodo-3,5-dimethylbenzene or 1-bromo-3,5-dimethylbenzene in C(6)D(6) and THF-d(8) to furnish 1-C(6)D(5)-3,5-Me(2)C(6)H(3), and 5-D-1,3-Me(2)C(6)H(3), respectively. Under similar conditions, the three-coordinate compound [(IPr)Fe(NHDipp)(2)] is inert toward these halides.
使用单齿 N-杂环卡宾作为辅助配体，合成了七种单核双（苯胺基）铁（II）配合物 [(IPr(2)Me(2))(2)Fe(NHAr)(2)]（IPr(2)Me(2) = 2,5-二异丙基-3,4-二甲基咪唑-1-亚基；Ar = Ph、C(6)H(4)-2-Pr(i)、Mes、C(6)H(3)-2,6-Cl(2)、Dipp）和 [(IPr)Fe(NHAr)(2)]（IPr = 2,5-二（2,6-二异丙基苯基）咪唑-1-亚基；Ar = C(6)H(3)-2,6-Cl(2)、Dipp）。这些高自旋二酰胺配合物通过Fe(Mes)(2)与相应的 N-杂环卡宾和苯胺的一锅反应制备而成。这些高自旋二酰胺配合物通过（1）H NMR、溶液磁化率、UV-vis、IR、X 射线衍射、循环伏安法以及元素分析等手段进行了全面的表征。N-杂环卡宾配体对亚铁中心的强亲和力以及 NHC 配体的空间位阻是稳定这些单核双（苯胺基）铁配合物的关键因素。反应性研究表明，四配位配合物[(IPr(2)Me(2))(2)Fe(NHMes)(2)]可以与 1 当量的 1-碘-3,5-二甲苯或 1-溴-3,5-二甲苯在 C(6)D(6)和 THF-d(8)中反应，分别生成 1-C(6)D(5)-3,5-Me(2)C(6)H(3)和 5-D-1,3-Me(2)C(6)H(3)。在类似条件下，三配位化合物[(IPr)Fe(NHDipp)(2)]对这些卤化物不反应。
