Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation
Online published: 2024-07-22
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
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 . DOI: 10.6023/A24060203
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