Citation: 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 Chimica Sinica, ;2017, 75(1): 92-98. doi: 10.6023/A16070364 shu

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

Department of Chemistry & Chemical Engineering, Shandong University, Jinan 250100, China

Corresponding author: Wang Wenguang, wwg@sdu.edu.cn
Received Date: 27 July 2016

Fund Project: National Natural Science Foundation of China 21402107National Natural Science Foundation of China 91427303the "1000 Youth Talents Plan" and National Undergraduate Training Programs for Innovation and Entrepreneurship 201510422032

Figures(8)

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.
- [FeFe] hydrogenase,
- diiron carbonyls,
- phosphine ligands,
- rotated structure,
- bridging CO ligand
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Azo-bridged New Diiron Carbonyl Complex: Synthesis of Fe2(NR)2-(CO)6-x(PR3)x and the Derivatives

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