Studies On Iron-sulfur Clusters Related To (C=S)NH

Hydrogenases are enzymes that can catalyze the proton reduction. They have received considerable attention due to their attractive application prospect in the new energy. Studies on biomimetic chemistry of hydrogenases have important theoretical significance, and show practical significance in hydrogen production in order to deal with the energy crisis and environment pollution. Iron-sulfur clusters are closely related to the active site of hydrogenases, so in this paper, a series of iron-sulfur clusters have been synthesized to investigate their structures and properties. And the results are as follows:1. Oxazolidine-2-thione compounds react with Fe3(CO)12 and Et3N in THF to afford metal complexes (μ-k2S,C-SC(O)NCH(CH2Ph)CH2OC)Fe2(CO)6(μ4-S)Fe2(CO)6 (μ-k2C,N-CH(CH2Ph) CH2OCN) (1), (μ3-S)2Fe3(CO)8(k1C-OCHRCH2NHC) (R= CH3, H; 2,3). Oxazolidine-2-thione reacts with electrophile reagents, Fe3(CO)12 and Et3N in THF to afford metal complexes (μ-RS)Fe2(CO)6(μ-k2C,N-CH2CH2OC=N)(R= CH3, CH2Ph; 4,5), (μ-k2P,S-Ph2PS)Fe2(CO)6 (μ-k2C,N-CH2CH2 OC=N) (6). These six metal complexes have been characterized by IR, NMR and X-ray crystallography. Electrochemical study of 1 and 4 reveals that compounds 1 and 4 can efficiently catalyze H2 evolution using HOAc as proton source.2. N-(2-pyridinyl) thioamide compounds react with Fe3(CO)i2 as 1:1 and 2:1 in THF to form metal complexes (μ-S)2C(CH3)Fe2(CO)6(μ-k1N-C5H4NNH) (7), Fe(CO)3(SC(CH3)NH C5H4N) (8), Fe(CO)3(SCHN(CHS)C5H4N) (10), Fe(CO)3(SCHNHC5H4N) (11), (μ-S)2 Fe2(CO)6 (μ-k2C,C-CHN(C5H4N)CH) (12), (μ-S)2Fe3(CO)9(μ-k2C,N-CHNHC5H4N) (13), N-(2-pyridinyl) thioamide compounds react with Fe3(CO)12 and Et3N as 2:1:1 in THF for half an hour, and then PPh2Cl is added to form metal complexes (μ-k2P,S-Ph2PS)Fe2(CO)6(μ-k2C,N-CH3C=NC5H4N) (9), (μ-k2P,S-Ph2PS)Fe2(CO)6 (μ-k2C,N-CH=NC5H4N) (14). These eight metal complexes have been characterized by IR, NMR and X-ray crystallography. Electrochemical study of 7,8,11 and 13 shows that these compounds can efficiently catalyze H2 evolution using HOAc as proton source.3. Thiocarbamates compounds react with Fe3(CO)12 and Et3N in THF for half an hour, and then the electrophilic reagents are added to obtain metal complexes (μ-SCH3)Fe2(CO)6(μ-k2C, N-ROC=NPh) (R= CH3, CH2CH3; 15,18), (μ-SCH2Ph)Fe2(CO)6(μ-k2C,N-ROC=NPh) (R= CH3, CH2CH3; 16,19), (μ-k2P,S-Ph2PS)Fe2(CO)6(μ-k2C,N-ROC=NPh) (R= CH3, CH2CH3; 17,20).These six metal complexes have been characterized by IR, NMR and X-ray crystallography. Electrochemical study of 19 demonstrates that compound 19 can efficiently catalyze H2 evolution using HOAc as proton source.