Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation

doi:10.6023/A24060203

Abstract

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

Cite this article

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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Fig. & Tab. 8

Figure 1. Some transition metal phosphorus clusters with NHC ligation

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

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]

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

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)]

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)]

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

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

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氮杂环卡宾配位的铁磷簇合物