基于偶氮桥连的新型双铁羰基配合物:Fe2(N2C5H10)(CO)6-x (PR3)x的合成及衍生

doi:10.6023/A16070364

摘要/Abstract

具有五元环结构的偶氮化合物4，4-二甲基-4，5-二氢-3H-吡咯（N₂C₅H₁₀），与Fe₃（CO）₁₂在甲苯中加热回流反应，生成双铁六羰基配合物Fe₂（N₂C₅H₁₀）（CO）₆（1）.反应中N=N双键被还原，配体以（N₂C₅H₁₀）^2-的形式与Fe^IFe^I配位，形成具有蝶形结构的34e^-化合物.研究了在脱羰基试剂Me₃NO存在条件下，1和单齿膦配体PR₃反应生成Fe₂（N₂C₅H₁₀）-（CO）₅（PR₃）（PR₃=PPh₃，2a；PCy₃，2b）单取代配合物.光照条件下，化合物1中的CO配体还可以被双齿膦配体dppe[dppe=1，2-C₂H₄（PPh₂）₂]和dppbz[dppbz=1，2-C₆H₄（PPh₂）₂]取代，生成产物的类型和膦配体的夹角相关.与夹角较大的dppe反应，生成桥连产物Fe₂（N₂C₅H₁₀）（CO）₄（μ-dppe）（3a）；而与刚性较大的dppbz反应时，Fe₂（NR）₂的蝶形结构打开呈四元环；其中一个Fe上的CO被取代，dppbz与该Fe中心螯合，生成具有桥连CO的化合物Fe₂（N₂C₅H₁₀）（μ-CO）（CO）₄（κ²-dppbz）（3b）.合成具有Fe^I-CO-Fe^I结构的羰基化合物，一直是模拟[FeFe]氢化酶活性中心还原态结构Fe₂（SR）₂（μ-CO）-（CO）_5-xL_x的重要挑战.该类Fe₂（NR）₂（CO）_6-x（PR₃）_x化合物的合成，能为探索模拟[FeFe]氢化酶活性中心结构提供新的途径和思路.以上化合物均通过核磁[³¹P（¹H）NMR]、红外光谱（IR）、元素分析及X射线单晶结构衍射等表征.

关键词: [FeFe]氢化酶, 双铁羰基配合物, 膦配体, 旋转构型, 桥联CO配体

Heating the toluene solution of 4,4-dimethyl-4,5-dihydro-3H-pyrazole (N₂C₅H₁₀) and Fe₃(CO)₁₂ at reflux for 1 h produces diiron hexacarbonyls Fe₂(N₂C₅H₁₀)(CO)₆ (1, ν_CO(CH₂Cl₂):2069, 2022, 1986 cm^-1). Compound 1 exhibits 34 e^- configuration, in which (N₂C₅H₁₀)^2- coordinates to diiron (Fe^IFe^I) centers featuring a butterfly structure. To a solution of 1 in toluene was added one equiv. of decarbonyl agent Me₃NO in MeCN, and the mixture was stirred at room temperature for 20 min. Then, one equiv. of monophosphine was added. After 3 h, the solvent was removed and the residue was extracted into 5 mL CH₂Cl₂. The product Fe₂(N₂C₅H₁₀)(CO)₅(PR₃) (PR₃=PPh₃, 2a; PCy₃, 2b) was obtained as brown crystals by allowing a pentane layer to diffuse into the CH₂Cl₂ solution at -20℃. ³¹P NMR spectra exhibit a singlet at δ 67 for 2a and δ 70 for 2b in CH₂Cl₂, respectively. In IR spectra, the ν_CO bands for 2a were displayed at 2032, 1968, 1952, 1907 cm^-1, which are compared to 2024, 1959, 1937, 1893 cm^-1 for 2b. Photolysis the toluene solution of 1 in the presence of chelating diphosphine ligands such as dppe[dppe=1,2-C₂H₄(PPh₂)₂] and dppbz[dppbz=1,2-C₆H₄(PPh₂)₂] affords diiron diphosphine carbonyl compounds. For dppe, the product was Fe₂(N₂C₅H₁₀)(CO)₄(μ-dppe) (3a, ³¹P NMR (CD₂Cl₂):δ 95, FT-IR (CH₂Cl₂, ν_CO):1984, 1940, 1925 and 1900 cm^-1), in which dppe is bridging the two iron centers. For more rigid diphosphine ligand dppbz, X-ray crystallographic analysis reveals the structure of Fe₂(N₂C₅H₁₀)(μ-CO)(CO)₄(dppbz)[3b, ³¹P NMR (CD₂Cl₂):δ 93]. In 3b, (N₂C₅H₁₀)^2- coordinates to diiron centers in a planar mode, and dppbz chelates at one Fe site by the replacement of one CO ligand. Compound 3b features a Fe-CO-Fe rotated structure with a bridging CO ligand between the two Fe centers. The ν_CO bands for 3b were displayed at 1990, 1947, 1919, 1895 cm^-1. With such a rotated structure, compound 3b provides a new approach for synthetic models of H_red state of [FeFe]-H₂ase. The CCDC number for 1, 2a, 2b, 3a and 3b are 1494954, 1494955, 1494956, 1494966 and 1494957. All the compounds were well characterized by NMR, IR spectroscopy and elemental analysis.

Key words: [FeFe] hydrogenase, diiron carbonyls, phosphine ligands, rotated structure, bridging CO ligand

引用此文

李冉, 徐文元, 赵巾钦, 余鑫, 王文光, 佟振合. 基于偶氮桥连的新型双铁羰基配合物:Fe₂(N₂C₅H₁₀)(CO)_6-x (PR₃)_x的合成及衍生[J]. 化学学报, 2017, 75(1): 92-98.

Li Ran, Xu Wenyuan, Zhao Jinqin, Yu Xin, Wang Wenguang, Tung Chen-Ho. Azo-bridged New Diiron Carbonyl Complex: Synthesis of Fe₂(NR)₂-(CO)_6-x(PR₃)_x and the Derivatives[J]. Acta Chim. Sinica, 2017, 75(1): 92-98.

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基于偶氮桥连的新型双铁羰基配合物:Fe₂(N₂C₅H₁₀)(CO)_6-x (PR₃)_x的合成及衍生

Azo-bridged New Diiron Carbonyl Complex: Synthesis of Fe₂(NR)₂-(CO)_6-x(PR₃)_x and the Derivatives

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