网络出版日期: 2024-07-22
Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation
Online published: 2024-07-22
通过三配位零价铁配合物[(NHC)Fe(η2:η2-dvtms)] (NHC=氮杂环卡宾; dvtms=四甲基二乙烯基二硅氧烷)与白磷的反应合成了三种氮杂环卡宾配位的铁磷簇合物, 对其进行了结构和光谱学表征. 通过分步重结晶的方法从[(IMes)Fe(η2:η2-dvtms)] (IMes=1,3-双(2,4,6-三甲基苯基)咪唑-2-亚基)与等物质的量的P4在低温下(－30 ℃到室温)的反应中分离到了三种铁磷簇合物[(IMes)2Fe2(μ-η5:η5-cyclo-P5)] (1)、[(IMes)3Fe3(μ-η6:η6:η6-P9)] (2)和[(IMes)2Fe2(μ-η2:η2-cyclo- P4P(IMes))(μ-η3:η3-P3)] (3). 配合物1和3可分别以18%和32%的产率从该零价铁配合物与等物质的量的P4在80 ℃和低温下的反应中分离得到. 配合物2仅能得到痕量的晶体. 这些配合物的结构均通过单晶X射线衍射表征. 配合物1为反三明治型的双核铁配合物. Fe…Fe距离为0.2515(1) nm, 其桥联μ-η5:η5-cyclo-P5配体乱序, 结构类似的配合物[(IDep)2Fe2(μ-η5:η5-cyclo-P5)] [4, IDep=1,3-双(2,6-二乙基苯基)咪唑-2-亚基]可通过[(IDep)Fe(η2:η2-dvtms)]与P4反应合成. 其单晶X射线衍射所得的结构中桥联μ-η5:η5-cyclo-P5配体无乱序现象, 两个铁中心具有相同的配位环境. 配合物1在80 K下的零场57Fe穆斯堡尔谱仅含一组四极距分裂的双峰, 同质异能位移δ=0.32 mm•s−1, 四极距裂分|ΔEQ|=0.61 mm•s−1. 磁化率测试表明配合物1的基态自旋量子数S=1/2. 这些表征数据显示该类反三明治型的双铁配合物可看作是一个Robin-Day Ⅲ型混合价态配合物. 配合物2为首例具有P9配体的过渡金属磷簇合物. 其P9配体含两个相对的三角形P3面和三个船式P6面. 每个船式P6面与一个Fe(IMes)片段以η6-形式配位. Fe…Fe距离平均值为0.2626(1) nm. 配合物3中μ-η2:η2-cyclo-P4P(IMes)配体和μ-η3:η3-P3配体的结构参数与[(IMes)2Co2(μ-η2:η2-cyclo-P4P(iPr2Im))(μ-η3:η3-P3)]中相应配体相近. 1H NMR和31P NMR表征显示3为抗磁性化合物. 配合物3的零场57Fe穆斯堡尔谱同质异能位移δ=0.26 mm•s−1, 四极距裂分|ΔEQ|=0.91 mm•s−1.
杜牧 , 杨程博 , 陈琦 , 邓亮 . 氮杂环卡宾配位的铁磷簇合物[J]. 化学学报, 2024 , 82(9) : 932 -939 . DOI: 10.6023/A24060203
Three iron phosphorus clusters with N-heterocyclic carbene ligation have been synthesized from the reactions of low-coordinate iron(0) complexes [(NHC)Fe(η2:η2-dvtms)] (NHC=N-heterocyclic carbene, dvtms=divinyltetramethyl- isiloxane) with white phosphorus and characterized by spectroscopic methods. The iron phosphorus clusters [(IMes)2Fe2(μ- η5:η5-cyclo-P5)] (1), [(IMes)3Fe3(μ-η6:η6:η6-P9)] (2) and [(IMes)2Fe2(μ-η2:η2-cyclo-P4P(IMes))(μ-η3:η3-P3)] (3) were isolated from the equimolar reaction of [(IMes)Fe(η2:η2-dvtms)] (IMes=1,3-dimesitylimidazol-2-ylidene) with P4 at low temperature (－30 ℃ to room temperature) upon recrystallization. Complexes 1 and 3 can be synthesized in 18% and 32% isolated yields, respectively, from the reactions of [(IMes)Fe(η2:η2-dvtms)] with P4 at different reaction temperature (80 ℃ and －30 ℃ to room temperature, respectively). Complex 2 can only be obtained in trace amount from the low-temperature reaction. The three iron phosphorus clusters 1~3 have been characterized by single-crystal X-ray diffraction studies. Complex 1 shows an anti-sandwich type structure with the Fe…Fe distance of 0.2515(1) nm and the μ-η5:η5-P5 ligand in disorder. Analogous com-plex [(IDep)2Fe2(μ-η5:η5-P5)] [4, IDep=1,3-di(2',6'-diethylphenyl)imidazol-2-ylidene] can be synthesized from the reaction of [(IDep)Fe(η2:η2-dvtms)] with P4. Its molecular structure established by X-ray diffraction study does not exhibit disorder in the μ-η5:η5-P5 ligand and the two iron centers show nearly identical coordination environment. The zero-field 57Fe Mössbauer spectrum of 1 measured at 80 K shows a quadrupole doublet with the isomer shift δ=0.32 mm•s−1 and quadrupole splitting |ΔEQ|=0.61 mm•s−1. Magnetic susceptibility measurements point out a doublet state (S=1/2) for 1. The characterization data suggests that 1 and 4 can be described as the III-type mixed valence complex based on the Robin-Day Models. Complex 2 represents the first example of metal complexes featuring a P9 ligand. The polyphosphide ligand contains two paralleling P3 triangles and three boat-shaped P6 faces. Each P6 face is coordinating with a Fe(IMes) fragment in η6-fashion. The three Fe atoms form a Fe3 triangle with the Fe…Fe distances close to each other [0.2626(1) nm in average]. Complex 3 features a μ-η2:η2-cyclo-P4P(IMes) ligand and a μ-η3:η3-P3 ligand. The bond distances and angles of the two polyphosphide ligands in 3 are close to those of the counterparts in [(IMes)2Co2(μ-η2:η2-cyclo-P4P(iPr2Im))(μ-η3:η3-P3)]. The 1H NMR and 31P NMR spectra of 3 are indicative of its diamagnetic nature. The 57Fe Mössbauer quadrupole doublet of 3 measured at 80 K has a isomer shift δ=0.26 mm•s－1 and quadrupole splitting |ΔEQ|=0.91 mm•s－1.
Key words： N-heterocyclic carbene; iron; white phosphorus; cluster compound; polyphosphide
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