Mono‐ and Bis‐Alkynyl Iron Complexes Supported by a “Softened” Tetraaza Macrocycle
Mono‐ and Bis‐Alkynyl Iron Complexes Supported by a “Softened” Tetraaza Macrocycle
复制标题
“软化”四氮杂大环支持的单炔基铁配合物和双炔基铁配合物
DOI：
10.1002/ejic.202101021
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发表时间：
2022
影响因子：
2.3
通讯作者：
Ren, Tong
中科院分区：
文献类型：
--
作者：
Clendening, Reese A.;Ren, Tong
本文描述了一对新型 Fe-炔基配合物 [FeIII(HMTI)(C2SiEt3)2]ClO4(2) 和 [FeII(HMTI)(C2SiEt3)(NCCH3)]ClO4(3)。 Fe(meso-HMC)Cl(ClO4)]ClO4(1) 与锂化三乙基甲硅烷基乙炔反应，随后暴露于氧气中，生成含有脱氢四亚胺大环 (HMTI) 的双炔基 2。在乙腈中用苔藓锌还原 2，得到单炔基 3。使用单晶X射线衍射确定了2和3的结构。对可见光吸收和电化学数据的分析确定了 HMTI 大环的氧化还原活性性质，并表明 Fedπ 和四亚胺 π* 轨道之间存在显着的相互作用。这些推论得到了密度泛函理论计算的进一步支持。
A pair of novel Fe‐alkynyl complexes, [FeIII(HMTI)(C2SiEt3)2]ClO4(2) and [FeII(HMTI)(C2SiEt3)(NCCH3)]ClO4(3), is described herein. Reaction of Fe(meso‐HMC)Cl(ClO4)]ClO4(1) with lithiated triethylsilylacetylene and subsequent exposure to oxygen yielded the bis‐alkynyl2containing the dehydrogenated tetraimine macrocycle (HMTI). Reduction of2by mossy zinc in acetonitrile yielded the mono‐alkynyl3. The structures of2and3were determined using single‐crystal X‐ray diffraction. Analysis of visible absorption and electrochemical data establishes the redox‐active nature of the HMTI macrocycle, and indicates significant interactions between the Fedπ and tetraimine π* orbitals. These deductions are further supported by density functional theory calculations.