氮杂环卡宾配位的铁磷簇合物

doi:10.6023/A24060203

摘要/Abstract

通过三配位零价铁配合物[(NHC)Fe(η²:η²-dvtms)] (NHC = N-heterocyclic carbene; dvtms = divinyltetramethylisiloxane)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的表征。通过分步重结晶的方法从[(IMes)Fe(η²:η²-dvtms)] （IMes = 1,3-dimesitylimidazol-2-ylidene）与等摩尔量P₄在低温下（-30 ℃到室温）的反应中分离到三种铁磷簇合物[(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摩尔量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2.515(1) Å,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-di(2’,6’-diethylphenyl)imidazol-2-ylidene) 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 |ΔE_Q| = 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2.626(1) Å。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。核磁氢谱和磷谱表征显示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 |ΔE_Q| = 0.91 mm•s^-1。

关键词: 氮杂环卡宾, 铁, 白磷, 簇合物, 多磷化物

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 = divinyltetramethylisiloxane) with white phosphorus and have been 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 2.515(1) Å and the μ-η⁵:η⁵-P₅ligand in disorder. Analogous complex [(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 |ΔE_Q| = 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 P₉ligand. 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 (2.626(1) Å 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 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 |ΔE_Q| = 0.91 mm•s^-1.

Key words: N-heterocyclic carbene, iron, white phosphorus, cluster compounds, polyphosphide

引用此文

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, doi: 10.6023/A24060203.

Du Mu, Yang Chengbo, Chen Qi, Deng Liang. Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation[J]. Acta Chimica Sinica, doi: 10.6023/A24060203.

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