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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, νCO(CH2Cl2):2069, 2022, 1986 cm-1). Compound 1 exhibits 34 e- configuration, in which (N2C5H10)2- coordinates to diiron (FeIFeI) 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 νCO 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, νCO):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 νCO 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 Hred 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.
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