The N-acylated derivatives of parent complex [{(μ-SCH2) 2NH}Fe2(CO)6] as active site models of fe-only hydrogenases: Synthesis, characterization, and related properties

Li Cheng Song, Liang Xing Wang, Bang Shao Yin, Yu Long Li, Xiao Guang Zhang, Yuan Wei Zhang, Xiang Luo, Qing Mei Hu

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Abstract

A series of N-acylated diiron azadithiolate complexes as H-cluster models was synthesized and structurally characterized. Treatment of parent complex [{(μ-SCH2)2NH}Fe2(CO)6] (A) with 2-chloroacetic acid in the presence of dicyclohexylcarbodiimide or with 2-chloroacetyl chloride in the presence of Et3N gave N-chloroacetyl complex [{(μ-SCH2)2NC(O)CH2Cl}Fe 2(CO)6] (1). Further treatment of 1 with MeC(O)SK afforded N-acetylthioacetyl complex [{(μ-SCH2)2NC(O)CH 2SC(O)Me}Fe2(CO)6] (2). N-Ethoxylcarbonylacetyl complex [{(μ-SCH2)2NC(O)CH2CO 2Et}Fe2(CO)6] (3) and N-heterocyclic complexes [{(μ-SCH2)2NC(O)C4H3Y-2}Fe 2(CO)6] (4, Y = O; 5, Y = S) were produced by reactions of A with EtO2CCH2C(O)Cl, 2-furancarbonyl chloride, and 2-thiophenecarbonyl chloride in the presence of pyridine or Et3N. Similarly, N-malonyl complex [{Fe2(CO)6(μ-SCH 2)2NC(O)}2CH2] (6) and N-carbonylbenzaldehyde complex [{(μ-SCH2)2NC(O)C 6H4CHO-P}Fe2(CO)6] (7) could be obtained by reaction of A with malonyl dichloride in the presence of pyridine and with p-CHOC6H4C(O)Cl in the presence of Et 3N. More interestingly, further reaction of 7 with PhCHO and pyrrole in a 1:3:4 molar ratio in the presence of BF3·OEt2 followed by p-chloranil yielded the first light-driven type of model complex containing an N-carbonylphenylporphyrin moiety [{(μ-SCH2) 2NC(O)(TPP)}Fe2(CO)6] (8, TPP = tetraphenylporphyrin group). Whereas the molecular structures of 2, 5, and 7 were established by X-ray crystallography, the electrochemical properties of 2-5 as well as the proton reduction to hydrogen gas catalyzed by 2 and 3 were studied by CV techniques.

Original languageEnglish (US)
Pages (from-to)291-297
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number2
DOIs
StatePublished - Jan 25 2008
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Keywords

  • Bioinorgnic chemistry
  • Electrochemistry
  • Hydrogenase models
  • Iron

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