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=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|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|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=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-P₅ligand 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 |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 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 |ΔE_Q|=0.91 mm•s^－1.

Key words: N-heterocyclic carbene, iron, white phosphorus, cluster compound, 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, 2024, 82(9): 932-939.

Mu Du, Chengbo Yang, Qi Chen, Liang Deng. Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation[J]. Acta Chimica Sinica, 2024, 82(9): 932-939.

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图/表 8

图1. 氮杂环卡宾配位的过渡金属磷簇合物

Figure 1. Some transition metal phosphorus clusters with NHC ligation

图式1. [(NHC)Fe(η2:η2-dvtms)]与白磷的反应及铁磷簇合物间的转化

Scheme 1. Reactions of [(NHC)Fe(η2:η2-dvtms)] with P4 and the transformations of the resultant iron polyphosphorus clusters

图2. (a)配合物[(IMes)2Fe2(μ-η5:η5-P5)] (1)和(b) [(IDep)2Fe2(μ-η5:η5-P5)] (4)的分子结构(氢原子已省略) [1中部分键长(nm)和键角(°): Fe(1)—Fe(1)#1 0.2515(1), Fe(1)—C(1) 0.1998(4), C(1)—Fe(1)—Fe(1)#1 180.0; 4中部分键长(nm)和键角(°): Fe(1)—Fe(2) 0.2516(1), Fe(1)—P(1) 0.2256(1), Fe(1)—P(2) 0.2306(1), Fe(1)—P(3) 0.2262(1), Fe(1)—P(4) 0.2282(1), Fe(1)—P(5) 0.2289(2), Fe(1)—C(1) 0.1973(5), Fe(2)—P(1) 0.2272(1), Fe(2)—P(2) 0.2298(1), Fe(2)—P(3) 0.2254(1), Fe(2)—P(4) 0.2298(1), Fe(2)—P(5) 0.2273(1), Fe(2)—C(2) 0.1998(5), P(1)—P(2) 0.2217(2), P(1)—P(5) 0.2262(2), P(2)—P(3) 0.2234(3), P(3)—P(4) 0.2263(2), P(4)—P(5) 0.2195(2), C(1)—Fe(1)—Fe(2) 180.0]

Figure 2. (a) Molecular structures of [(IMes)2Fe2(μ-η5:η5-P5)] (1) and (b) [(IDep)2Fe2(μ-η5:η5-P5)] (4) (hydrogen atom has been omitted) [Selected bond distances (nm) and angles (°), for 1: Fe(1)—Fe(1)#1 0.2515(1), Fe(1)—C(1) 0.1998(4), C(1)—Fe(1)—Fe(1)#1 180.0; for 4: Fe(1)—Fe(2) 0.2516(1), Fe(1)—P(1) 0.2256(1), Fe(1)—P(2) 0.2306(1), Fe(1)—P(3) 0.2262(1), Fe(1)—P(4) 0.2282(1), Fe(1)—P(5) 0.2289(2), Fe(1)—C(1) 0.1973(5), Fe(2)—P(1) 0.2272(1), Fe(2)—P(2) 0.2298(1), Fe(2)—P(3) 0.2254(1), Fe(2)—P(4) 0.2298(1), Fe(2)—P(5) 0.2273(1), Fe(2)—C(2) 0.1998(5), P(1)—P(2) 0.2217(2), P(1)—P(5) 0.2262(2), P(2)—P(3) 0.2234(3), P(3)—P(4) 0.2263(2), P(4)—P(5) 0.2195(2), C(1)—Fe(1)—Fe(2) 180.0]

图3. 配合物1在80 K下的零场57Fe-穆斯堡尔谱

Figure 3. Zero-field 57Fe M?ssbauer spectrum of 1 measured at 80 K

图4. (a)配合物2的分子结构和(b)配合物2的P9骨架(氢原子已省略)[部分键长(nm)和键角(°): Fe(1)—Fe(2) 0.2625(1), Fe(1)—Fe(3) 0.2626(1), Fe(2)—Fe(3) 0.2627(1), Fe(1)—P(1) 2.349(2), Fe(1)—P(2) 0.2320(2), Fe(1)—P(3) 0.2331(2), Fe(1)—P(4) 0.2344(2), Fe(1)—P(5) 0.2331(2), Fe(1)—P(6) 0.2322(2), Fe(1)—C(1) 0.2006(6), P(1)—P(2) 0.2187(2), P(1)—P(3) 0.2176(2), P(2)—P(6) 0.2544(2), P(2)—P(8) 0.2516(2), P(3)—P(5) 0.2512(2), P(3)—P(9) 0.2554(2), P(4)—P(5) 0.2181(3), P(4)—P(6) 0.2175(2), P(5)—P(9) 0.2523(2), P(6)—P(8) 0.2529(2), P(7)—P(8) 0.2180(2), P(7)—P(9) 0.2173(3), Fe(2)—Fe(1)—Fe(3) 60.04(3), P(1)—Fe(1)—Fe(2) 56.17(5), P(1)—Fe(1)—Fe(3) 116.20(6)]

Figure 4. (a) Molecular structure of complex 2 and (b) P9 skeleton of complex 2 (hydrogen atoms have been omitted) [Selected bond distances (nm) and angles (°): Fe(1)—Fe(2) 0.2625(1), Fe(1)—Fe(3) 0.2626(1), Fe(2)—Fe(3) 0.2627(1), Fe(1)—P(1) 2.349(2), Fe(1)—P(2) 0.2320(2), Fe(1)—P(3) 0.2331(2), Fe(1)—P(4) 0.2344(2), Fe(1)—P(5) 0.2331(2), Fe(1)—P(6) 0.2322(2), Fe(1)—C(1) 0.2006(6), P(1)—P(2) 0.2187(2), P(1)—P(3) 0.2176(2), P(2)—P(6) 0.2544(2), P(2)—P(8) 0.2516(2), P(3)—P(5) 0.2512(2), P(3)—P(9) 0.2554(2), P(4)—P(5) 0.2181(3), P(4)—P(6) 0.2175(2), P(5)—P(9) 0.2523(2), P(6)—P(8) 0.2529(2), P(7)—P(8) 0.2180(2), P(7)—P(9) 0.2173(3), Fe(2)—Fe(1)—Fe(3) 60.04(3), P(1)—Fe(1)—Fe(2) 56.17(5), P(1)—Fe(1)—Fe(3) 116.20(6)]

图5. 配合物3的分子结构(氢原子已省略)[部分键长(nm)和键角(°): Fe(1)—Fe(2) 0.2657(1), Fe(1)—P(1) 0.2184(1), Fe(1)—P(2) 0.2397(1), Fe(1)—P(3) 0.2229 (2), Fe(1)—P(5) 0.2320 (1), Fe(1)—P(6) 0.2265(1), Fe(1)—C(1) 0.1981(5), Fe(2)—P(1) 0.2191(1), Fe(2)—P(2) 0.2418(1), Fe(2)—P(3) 0.2228(1), Fe(2)—P(4) 0.2331(1), Fe(2)—P(8) 0.2299(2), Fe(2)—C(2) 0.1979(5), P(1)—P(2) 0.2180(2), P(2)—P(3) 0.2157(2), P(4)—P(5) 0.2247(2), P(4)—P(8) 0.2131(2), P(5)—P(6) 0.2145(2), P(6)—P(7) 0.2210(2), P(7)—P(8) 0.2178(2), P(7)—C(3) 0.1831(6), P(3)—P(2)—P(1) 99.55(8)]

Figure 5. Molecular structure of complex 3 (hydrogen atoms have been omitted) [Selected bond distances (nm) and angles (°): Fe(1)—Fe(2) 0.2657(1), Fe(1)—P(1) 0.2184(1), Fe(1)—P(2) 0.2397(1), Fe(1)—P(3) 0.2229 (2), Fe(1)—P(5) 0.2320 (1), Fe(1)—P(6) 0.2265(1), Fe(1)—C(1) 0.1981(5), Fe(2)—P(1) 0.2191(1), Fe(2)—P(2) 0.2418(1), Fe(2)—P(3) 0.2228(1), Fe(2)—P(4) 0.2331(1), Fe(2)—P(8) 0.2299(2), Fe(2)—C(2) 0.1979(5), P(1)—P(2) 0.2180(2), P(2)—P(3) 0.2157(2), P(4)—P(5) 0.2247(2), P(4)—P(8) 0.2131(2), P(5)—P(6) 0.2145(2), P(6)—P(7) 0.2210(2), P(7)—P(8) 0.2178(2), P(7)—C(3) 0.1831(6), P(3)—P(2)—P(1) 99.55(8)]

图6. 配合物3在80 K下的零场57Fe-穆斯堡尔谱

Figure 6. Zro-field 57Fe M?ssbauer spectrum of 3 measured at 80 K

图式2. 铁磷簇合物1~3的可能形成路径

Scheme 2. Proposed formation routes for the iron polyphosphorus clusters 1~3

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