Reactions Starting from Diiron Propanedithiolate [(μ-SCH<sub>2</sub>)<sub>2</sub>CH(OH)]Fe<sub>2</sub>(CO)<sub>6</sub> Leading to Malonyl-, PPh<sub>3</sub>-, and [60]Fullerene-Containing Compounds Relevant to the Active Site of FeFe-Hydrogenases
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As the active site models of FeFe-hydrogenases, a series of new diiron propanedithiolate compounds (1−7) have been synthesized starting from [(μ-SCH2)2CH(OH)]Fe2(CO)6 (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine gave the malonyl-containing compounds [(μ-SCH2)2CHO2CCH2CO2Et]Fe2(CO)6 (1) and [Fe2(CO)6(μ-SCH2)2CHO2C]2CH2 (2) in 64% and 55% yields, respectively. While A reacted with PPh3 in the presence of Me3NO to give the PPh3-substituted compound [(μ-SCH2)2CH(OH)]Fe2(CO)5(PPh3) (3) in 91% yield, reaction of 3 with malonyl dichloride in the presence of pyridine produced the malonyl-containing compound [Fe2(CO)5(PPh3)(μ-SCH2)2CHO2C]2CH2 (4) in 67% yield. More interestingly, compounds 1, 2, and 4 could react with C60 in the presence of CBr4 and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel−Hirsch reaction to afford the [60]fullerene compounds [(μ-SCH2)2CHO2CC(C60)CO2Et]Fe2(CO)6 (5), [Fe2(CO)6(μ-SCH2)2CHO2C]2C(C60) (6), and [Fe2(CO)5(PPh3)(μ-SCH2)2CHO2C]2C(C60) (7) in 36−39% yields. While new compounds 1−7 were characterized by elemental analysis and various spectroscopic methods, 1−4 were further characterized by X-ray crystallography, and the photoinduced H2 evolution catalyzed by 5 was preliminarily investigated.
